Reduced inhalation hazard sanitizers and disinfectants via high molecular weight polymers

ABSTRACT

The invention provides antimicrobial compositions having reduced inhalation risks by combining ammonium compounds and polymers in combination with optional acid components, surfactants and/or additional functional ingredients. The antimicrobial compositions which have a reduced risk of inhalation. Methods of making and employing the compositions are disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. Ser. No.15/909,642, filed on Mar. 1, 2018, which claims priority under 35 U.S.C.§ 119 to provisional application U.S. Ser. No. 62/465,483, filed Mar. 1,2017, both of which are herein incorporated by reference in theirentirety.

FIELD OF THE INVENTION

The present invention relates to the field of aqueous compositions forcleaning, sanitizing, and disinfecting. In some embodiments, anantimicrobial quaternary ammonium compound is provided in combinationwith a polymer component provide a composition having reduced inhalationrisk coupled with the sanitizing, disinfectant and/or antimicrobialproperties. In other aspects, an antimicrobial quaternary ammoniumcompound is provided in combination with a surfactant component, apolymer component, and additional functional ingredients. In particular,the combination provides heightened antimicrobial activity and reducedinhalation risk as compared to either the surfactant or the quaternaryammonium compound alone. Beneficially, according to the invention thecleaning composition is provided according to a particular applicationof use.

BACKGROUND OF THE INVENTION

Antimicrobial agents are chemical compositions that are used to preventmicrobiological contamination and deterioration of products, materials,mediums (such as water process streams) and systems. Antimicrobialagents and compositions are used, for example, as disinfectants orsanitizers in association with hard surface cleaning, food preparation,animal feed, cooling water, hospitality services, hospital and medicaluses, pulp and paper manufacturing, cleaning textiles, and waterprocessing. Of the diverse categories of antimicrobial agents andcompositions, quaternary ammonium compounds represent one of the largestof the classes of agents in use. At low concentrations, quaternaryammonium type antimicrobial agents are bacteriostatic, fungistatic,algistatic, sporostatic, and tuberculostatic. At medium concentrationsthey are bactericidal, fungicidal, algicidal, and viricidal againstlipophilic viruses. However, at high concentrations, generally greaterthan about 2 to 3 wt. %, they demonstrate acute toxicity. According tothe United States Environmental Protection Agency, contact withquaternary ammonium compounds cause contact dermatitis and nasalirritation. Further, certain quaternary ammonium compounds arerespiratory sensitizers and are associated with asthma and otherrespiratory conditions. Personal protection and proper ventilation arerequired in handling and use of quaternary ammonium compounds in orderto limit the inhalation amount. Per the United States EnvironmentalProtection Agency Health Effects Test Guidelines, OPPTS 870.1300 forAcute Inhalation Toxicity, during the development of a generating systemfor such compositions, particle size analysis should be performed toestablish the stability of aerosol concentrations. The mass medianaerodynamic diameter particle size should be between 1-4 micrometers.The particle size of hydgroscopic materials should be small enough whendry to assure that the size of the swollen particle will still be withinthe 1-4 micrometer range. Further, spray devices create a spray patternof the composition that contacts the target hard surface. The majorityof the composition comes to reside on the target surface, while a smallportion of the sprayable composition may become an airborne aerosol ormist consisting of small particles (e.g. an airborne mist or finelydivided aerosol) of the cleaning composition that can remain suspendedor dispersed in the atmosphere surrounding the dispersal site for aperiod of time, such as between about 5 seconds to about 10 minutes.

Such airborne mist or finely divided aerosol generated during thespraying process can present a substantial problem

Such aqueous compositions having a strong base cleaning component in theform of a finely divided aerosol or mist can cause respiratory distressin a user. To alleviate the respiratory distress, some sprayable aqueouscompositions have been formulated with reduced quantities of thealkaline cleaning components. Strong caustic has been replaced byreduced alkalinity bases such as bicarbonate or by solvent materials.However, the reduction in concentration or substitution of thesematerials can often reduce the cleaning activity and effectiveness ofthe material when used. This necessitates the use of organic surfactantsor glycol, alkyl ether or dimethyl sulfoxide solvent materials toenhance the detergent properties of the reduced alkaline materials.Despite improvements seen in sprayable aqueous compositions thereremains a need for improved compositions having reduced misting andtherefore reduced inhalation, while providing efficacious cleaning,sanitizing and disinfecting.

Development and improvements to polymers for various uses include thosedisclosed in EP 202,780 disclosing particulate cross-linked copolymersof acrylamide with at least 5 mole percent dialkylaminoalkyl acrylate;U.S. Pat. No. 4,950,725 disclosing the addition of a cross-linking agentboth at the beginning, and during the polymerization process underconditions such that its availability for reaction is substantiallyconstant throughout the process; EP 374,458 disclosing water-solublebranched high molecular weight cationic polymers; EP 363,024 disclosingchain transfer agent at the conclusion of polymerization of aDADMAC/acrylamide copolymer; U.S. Pat. No. 4,913,775 disclosing use ofsubstantially linear cationic polymers such asacrylamide/dimethylaminoethyl acrylate methyl chloride quaternary saltcopolymers; U.S. Pat. No. 5,393,381 disclosing branched cationicpolyacrylamide powder such as an acrylamide/dimethylaminoethyl acrylatequaternary salt copolymer; and WO2002002662 disclosing water-solublecationic, anionic, and nonionic polymers, synthesized using water-in-oilemulsion, dispersion, or gel polymerization and having a fast rate ofsolubilization, higher reduced specific viscosities.

Therefore, it is an object of the invention to reduce inhalation risk ofsuch compositions at high, medium, and low concentrations. Reducedinhalation risk can also be measured indirectly by reduced aerosol masscollection from high volume air sampling. Reduced levels of masscorrelate directly to reduced inhalation. This reduction is distinctfrom a reduction in misting, which is determined from the droplet sizeof an applied solution, with an increased droplet size indicatingreduced misting and atomization. Indeed, an advantage of the liquidcompositions of the present invention is that the inhalation risk by theuser of said compositions is significantly reduced or diminished. Thus,the compositions herein avoid potential health issues like nose and/orthroat irritation and/or coughing or even lung damage, which mayotherwise occur from inhalation of quaternary ammonium compounds. Afurther advantage of the present invention is that also eye irritationand/or damage is prevented when using the cleaning compositionsaccording to the present invention.

Accordingly, it is an objective of the claimed invention to develop anenhanced antimicrobial quaternary ammonium compound-based composition.

It is a further object of the invention is a reduced inhalation productsuitable for formulation using polymers in neutral, acidic, and/or oralkaline formulations, including oxidizing formulations.

It is a further object of the invention to provide an effectiveantimicrobial quaternary ammonium compound-based composition that whenin contact with biological matter have a reduced risk of inhalation andexposure.

It is a further object of the invention to provide a synergisticcomposition of a quaternary ammonium compounds and additional functionalingredients to provide such improvements on acute toxicity levels.

It is an object of the invention to provide an activated composition,having reduced acute toxicity and inhalation risk, having application ofuse including, for example, hard surface sanitizers, facilitysanitizers, water treatment, disinfectant and/or sanitizing surfaces,including high level disinfectants for medical instruments,antimicrobial lubricants, laundry cleaning and sanitizing,antimicrobials having enhanced mildness and reduced irritancy, enhancedcombination products, third sink applications, and the like whereantimicrobial quaternary ammonium compounds are used.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

The compositions according to the invention provides the ability tomaintain equal or enhanced antimicrobial efficacy of quaternary ammoniumcompounds while simultaneously reducing inhalation risk as a result ofincorporation of high molecular weight emulsion and dispersion polymersin the compositions.

In an aspect, a concentrated cleaning composition according to thedisclosure comprises a cleaning component comprising a disinfectant,sanitizer, antimicrobial compound, or combinations thereof; and apolymer component, wherein said polymer is a high molecular weightcationic, nonionic, or anionic polymer. According to the disclosure, thecleaning component is a quaternary ammonium compound, an acid sanitizer,an oxidizer, an amine, or combinations thereof; while the polymercomponent is an inversion emulsion polymer, dispersion polymer, powderpolymer, xanthan gum, or combinations thereof.

In an aspect, a cleaning composition according to the disclosurecomprises a cleaning component of a quaternary ammonium compound, and apolymer component of a high molecular weight cationic or anionicinversion emulsion polymer; a high molecular weight cationic or anionicdispersion polymer; or a high molecular weight cationic or anionicpowder polymer.

In a further aspect, a cleaning composition according to the disclosurecomprises a cleaning component of an acid sanitizer, and a polymercomponent of a high molecular weight cationic, anionic, or nonionicinversion emulsion polymer; a high molecular weight cationic, anionic,or nonionic dispersion polymer; a high molecular weight cationic,anionic, or nonionic powder polymer; or xanthan gum.

In a still further aspect, a cleaning composition according to thedisclosure comprises a cleaning component of an oxidizer, and polymercomponent of a high molecular weight cationic, anionic, or nonionicinversion emulsion polymer; a high molecular weight cationic, anionic,or nonionic dispersion polymer; a high molecular weight cationic,anionic, or nonionic powder polymer; or xanthan gum.

In a still further aspect, a cleaning composition according to thedisclosure comprises a cleaning component of an amine, and a polymercomponent of a high molecular weight cationic, anionic, or nonionicinversion emulsion polymer; a high molecular weight cationic, anionic,or nonionic dispersion polymer; a high molecular weight cationic,anionic, or nonionic powder polymer; or xanthan gum.

The cleaning compositions according to the disclosure may comprise apolymer component with a molecular weight of 1 million Da to 25 millionDa; a particular size ranging from 0.1 to 10 microns; and a viscosity of50 to 5000 cPs. Further, the cleaning compositions may further comprisean acid component, wherein the acid component is present in an amountfrom about 0.1 wt.-% to about 30 wt.-%, and wherein the acid componentprovides pH control so that cleaning composition has a pH from 0-6.Still further, the cleaning compositions according to the disclosure mayfurther comprise at least one anionic surfactant, nonionic surfactant,amphoteric surfactant, or combinations thereof, wherein the at least onesurfactant is present in an amount from about 0.1 wt.-% to about 30wt.-%.

The cleaning compositions according to the disclosure may furthercomprise at least one additional functional ingredient selected from thegroup consisting of additional surfactants, thickeners and/or viscositymodifiers, solvents, solubility modifiers, humectants, metal protectingagents, stabilizing agents, corrosion inhibitors, sequestrants and/orchelating agents, solidifying agent, sheeting agents, pH modifyingcomponents, fragrances and/or dyes, hydrotropes or couplers, buffers,and combinations thereof.

In an aspect of the disclosure, the cleaning compositions provide atleast 4 log kill on treated surfaces will providing reduced inhalationrisk. Further, the cleaning compositions provide reduced inhalation riskwith a median particle size of said composition is about 11 microns orgreater.

In a further aspect of the disclosure, a cleaning composition comprisesa quaternary ammonium compound having the formula:

wherein groups R1, R2, R3, and R4 each have less than a C20 chainlength, and X- is an anionic counterion; and a polymer component,wherein said polymer component is a high molecular weight cationic ornonionic polymer; wherein the composition is either a ready to usesolution or water soluble concentrate and has a pH between about 0 toabout 6.

According to an aspect of the disclosure, the quaternary ammoniumcompound is selected from the group consisting of monoalkyltrimethylammonium salts, monoalkyldimethylbenzyl ammonium salts, dialkyldimethylammonium salts, heteroaromatic ammonium salts, polysubstitutedquaternary ammonium salts, bis-quaternary ammonium salts, polymericquaternary ammonium salts, and combinations thereof. In a further aspectof the disclosure, the quaternary ammonium compound is present in anamount from about 1 wt.-% to about 50 wt.-%.

In an aspect of the disclosure, the polymer component has a molecularweight of 1 million Da to 25 million Da; a particle size ranging from0.1 to 10 microns; and a viscosity of 50 to 5000 cPs. Still further, thepolymer component is acrylamide, methacrylamide, acrylic acid or itssalts, N-t-butyl acrylamide sulfonic acid (ATBS) or its salts,acrylamide tertiary butyl sulfonic acid or its salts,2-(acryloyloxy)-N,N,N-trimethylethananminium (DMAEA.MCQ),diallyldimethylammonium chloride, dimethylaminoethyl acrylate methylchloride quaternary salt, acrylamidopropyltrimethylammonium chloride,dimethylaminoethyl methacrylate methyl chloride quaternary salt,methacrylamidopropyltrimethylammonium chloride, or combinations of thesame.

In an aspect of the disclosure, the cleaning composition furthercomprises an acid component, wherein the acid component is present in anamount from about 0.1 wt.-% to about 30 wt.-% and provides pH control sothat cleaning composition has a pH from 0-6. In a further aspect of thedisclosure, the cleaning composition further comprises at least oneanionic surfactant, nonionic surfactant, amphoteric surfactant orcombinations thereof, wherein the at least one surfactant is present inan amount from about 0.1 wt.-% to about 30 wt.-%.

In a still further aspect of the disclosure, the cleaning compositionfurther comprises at least one additional functional ingredient selectedfrom the group consisting of additional surfactants, thickeners and/orviscosity modifiers, solvents, solubility modifiers, humectants, metalprotecting agents, stabilizing agents, corrosion inhibitors,sequestrants and/or chelating agents, solidifying agent, sheetingagents, pH modifying components, fragrances and/or dyes, hydrotropes orcouplers, buffers, and combinations thereof.

The cleaning compositions according to the disclosure provides at least4 log kill on treated surfaces while providing reduced inhalation risk.Further, the cleaning compositions according to the disclosure providereduced inhalation risk with a median particle size of said compositionis about 11 microns or greater.

Methods of employing the compositions are also included in theembodiments of the invention. In an aspect of the disclosure, the methodof killing microbes comprises applying to a substrate a cleaningcomposition according to the disclosure, wherein the compositionprovides at least 4 log kill on treated surfaces while providing areduced inhalation risk.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The embodiments of this invention are not limited to particularcompositions, methods of making and/or methods of employing the same forhard surface sanitizing and disinfecting, including antimicrobial and/orsanitizing application for cleaning compositions, along with alternativecleaning and uses for cleaning compositions, which can vary and areunderstood by skilled artisans. So that the invention may be morereadily understood, certain terms are first defined. It is further to beunderstood that all terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers defining the range and include each integer within the definedrange. Throughout this disclosure, various aspects of this invention arepresented in a range format. It should be understood that thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of theinvention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges, fractions,and individual numerical values within that range. For example,description of a range such as from 1 to 6 should be considered to havespecifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well asindividual numbers within that range, for example, 1, 2, 3, 4, 5, and 6,and decimals and fractions, for example, 1.2, 3.8, 1½, and 4¾ Thisapplies regardless of the breadth of the range.

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

As used herein, the term “about” refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term or abbreviation “AcAm” refers to acrylamide.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the terms “active chlorine”, “chlorine”, and“hypochlorite” are all used interchangeably and are intended to meanmeasurable chlorine available in a use solution as evaluated by standardtitration techniques known to those of skill in the art. In a preferredaspect, the inverse emulsion polymer compositions provide chlorine-freecleaning compositions.

As used herein, the terms “aerosol” and “mist” refer to airbornedispersions of small particles comprising the cleaning composition thatcan remain suspended or dispersed in the atmosphere surrounding acleaning site for at least 5 seconds, more commonly 15 seconds to 10minutes.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism. For the purpose of this patent application, successfulmicrobial reduction is achieved when the microbial populations arereduced by at least about 50%, or by significantly more than is achievedby a wash with water. Larger reductions in microbial population providegreater levels of protection.

The term or abbreviation “DADMAC” refers to diallyldimethylammoniumchloride.

The term or abbreviation “DMAEA” refers to dimethylaminoethyl acrylate.

The term or abbreviation “DMAEM” refers to dimethylaminoethylmethacrylate.

The term or abbreviation “DMAEA BCQ” refers to dimethylaminoethylacrylate, benzyl chloride quaternary salt.

The term or abbreviation “DMAEA′MCQ” refers to dimethylaminoethylacrylate, methyl chloride quaternary salt.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). According to this reference adisinfectant should provide a 99.999% reduction (5-log order reduction)within 30 seconds at room temperature, 25±2° C., against several testorganisms. According to embodiments of the invention, a disinfectingcomposition provides a 99.999% reduction (5-log order reduction) of thedesired organisms (including bacterial contaminants) at a usetemperature. Further, a disinfectant should provide a 99.99% reduction(4-log order reduction) within 30 seconds at room temperature, 25±2° C.,against several test organisms. According to embodiments of theinvention, a disinfecting composition provides a 99.99% reduction (4-logorder reduction) of the desired organisms (including bacterialcontaminants) at a use temperature. Further, a disinfectant shouldprovide a 99.9% reduction (3-log order reduction) within 30 seconds atroom temperature, 25±2° C., against several test organisms. According toembodiments of the invention, a disinfecting composition provides a99.9% reduction (3-log order reduction) of the desired organisms(including bacterial contaminants) at a use temperature. As used herein,the term “high level disinfection” or “high level disinfectant” refersto a compound or composition that kills substantially all organisms,except high levels of bacterial spores, and is effected with a chemicalgermicide cleared for marketing as a sterilant by the Food and DrugAdministration. As used herein, the term “intermediate-leveldisinfection” or “intermediate level disinfectant” refers to a compoundor composition that kills mycobacteria, most viruses, and bacteria witha chemical germicide registered as a tuberculocide by the EnvironmentalProtection Agency (EPA). As used herein, the term “low-leveldisinfection” or “low level disinfectant” refers to a compound orcomposition that kills some viruses and bacteria with a chemicalgermicide registered as a hospital disinfectant by the EPA. The term orabbreviation “EDTA 4Na+” refers to ethylenediaminetetraacetic acid,tetrasodium salt.

As used herein, the phrase “food processing surface” refers to a surfaceof a tool, a machine, equipment, a structure, a building, or the likethat is employed as part of a food processing, preparation, or storageactivity. Examples of food processing surfaces include surfaces of foodprocessing or preparation equipment (e.g., slicing, canning, ortransport equipment, including flumes), of food processing wares (e.g.,utensils, dishware, wash ware, and bar glasses), and of floors, walls,or fixtures of structures in which food processing occurs. Foodprocessing surfaces are found and employed in food anti-spoilage aircirculation systems, aseptic packaging sanitizing, food refrigerationand cooler cleaners and sanitizers, ware washing sanitizing, blanchercleaning and sanitizing, food packaging materials, cutting boardadditives, third-sink sanitizing, beverage chillers and warmers, meatchilling or scalding waters, autodish sanitizers, sanitizing gels,cooling towers, food processing antimicrobial garment sprays, andnon-to-low-aqueous food preparation lubricants, oils, and rinseadditives.

As used herein, the phrase “food product” includes any food substancethat might require treatment with an antimicrobial agent or compositionand that is edible with or without further preparation. Food productsinclude meat (e.g. red meat and pork), seafood, poultry, produce (e.g.,fruits and vegetables), eggs, living eggs, egg products, ready to eatfood, wheat, seeds, roots, tubers, leafs, stems, corns, flowers,sprouts, seasonings, or a combination thereof. The term “produce” refersto food products such as fruits and vegetables and plants orplant-derived materials that are typically sold uncooked and, often,unpackaged, and that can sometimes be eaten raw.

The term “hard surface” refers to a solid, substantially non-flexiblesurface such as a counter top, tile, floor, wall, panel, window,plumbing fixture, kitchen and bathroom furniture, appliance, engine,circuit board, and dish. Hard surfaces may include for example, healthcare surfaces and food processing surfaces.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of electronicapparatus employed for monitoring patient health, and of floors, walls,or fixtures of structures in which health care occurs. Health caresurfaces are found in hospital, surgical, infirmity, birthing, mortuary,and clinical diagnosis rooms. These surfaces can be those typified as“hard surfaces” (such as walls, floors, bed-pans, etc.), or fabricsurfaces, e.g., knit, woven, and non-woven surfaces (such as surgicalgarments, draperies, bed linens, bandages, etc.,), or patient-careequipment (such as respirators, diagnostic equipment, shunts, bodyscopes, wheel chairs, beds, etc.,), or surgical and diagnosticequipment. Health care surfaces include articles and surfaces employedin animal health care.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning with acomposition according to the present invention.

As used herein, the phrases “medical instrument,” “dental instrument,”“medical device,” “dental device,” “medical equipment,” or “dentalequipment” refer to instruments, devices, tools, appliances, apparatus,and equipment used in medicine or dentistry. Such instruments, devices,and equipment can be cold sterilized, soaked or washed and then heatsterilized, or otherwise benefit from cleaning in a composition of thepresent invention.

These various instruments, devices and equipment include, but are notlimited to: diagnostic instruments, trays, pans, holders, racks,forceps, scissors, shears, saws (e.g. bone saws and their blades),hemostats, knives, chisels, rongeurs, files, nippers, drills, drillbits, rasps, burrs, spreaders, breakers, elevators, clamps, needleholders, carriers, clips, hooks, gouges, curettes, retractors,straightener, punches, extractors, scoops, keratomes, spatulas,expressors, trocars, dilators, cages, glassware, tubing, catheters,cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, andarthroscopes) and related equipment, and the like, or combinationsthereof.

As used herein, the term “microbe” is synonymous with microorganism. Forthe purpose of this patent application, successful microbial reductionis achieved when the microbial populations are reduced by at least about50%, or by significantly more than is achieved by a wash with water.Larger reductions in microbial population provide greater levels ofprotection. Differentiation of antimicrobial “-cidal” or “-static”activity, the definitions which describe the degree of efficacy, and theofficial laboratory protocols for measuring this efficacy areconsiderations for understanding the relevance of antimicrobial agentsand compositions. Cleaning compositions can affect two kinds ofmicrobial cell damage. The first is a lethal, irreversible actionresulting in complete microbial cell destruction or incapacitation. Thesecond type of cell damage is reversible, such that if the organism isrendered free of the agent, it can again multiply. The former is termedmicrobiocidal and the later, microbiostatic. A sanitizer and adisinfectant are, by definition, agents which provide antimicrobial ormicrobiocidal activity. In contrast, a preservative is generallydescribed as an inhibitor or microbiostatic composition.

As used herein, the term “microorganism” refers to any noncellular orunicellular (including colonial) organism. Microorganisms include allprokaryotes. Microorganisms include bacteria (including cyanobacteria),spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, andsome algae. As used herein, the term “sanitizer” refers to an agent thatreduces the number of bacterial contaminants to safe levels as judged bypublic health requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25±2° C., against several test organisms. According toembodiments of the invention, a sanitizing composition provides a99.999% reduction (5-log order reduction) of the desired organisms(including bacterial contaminants) at a use temperature. Further, asanitizer should provide a 99.99% reduction (4-log order reduction)within 30 seconds at room temperature, 25±2° C., against several testorganisms. According to embodiments of the invention, a sanitizingcomposition provides a 99.99% reduction (4-log order reduction) of thedesired organisms (including bacterial contaminants) at a usetemperature. Further, a sanitizer should provide a 99.9% reduction(3-log order reduction) within 30 seconds at room temperature, 25±2° C.,against several test organisms. According to embodiments of theinvention, a sanitizing composition provides a 99.9% reduction (3-logorder reduction) of the desired organisms (including bacterialcontaminants) at a use temperature. Differentiation of antimicrobial“-cidal” or “-static” activity, the definitions which describe thedegree of efficacy, and the official laboratory protocols for measuringthis efficacy are considerations for understanding the relevance ofantimicrobial agents and compositions. Cleaning compositions can affecttwo kinds of microbial cell damage. The first is a lethal, irreversibleaction resulting in complete microbial cell destruction orincapacitation. The second type of cell damage is reversible, such thatif the organism is rendered free of the agent, it can again multiply.The former is termed microbiocidal and the later, microbiostatic. Asanitizer and a disinfectant are, by definition, agents which provideantimicrobial or microbiocidal activity. In contrast, a preservative isgenerally described as an inhibitor or microbiostatic composition.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbiostatic. A sanitizer and a disinfectant are, bydefinition, agents which provide antimicrobial or microbiocidalactivity. In contrast, a preservative is generally described as aninhibitor or microbiostatic composition

The term “surfactant” as used herein is a compound that contains alipophilic segment and a hydrophilic segment, which when added to wateror solvents, reduces the surface tension of the system.

The term “viscosity” is used herein to describe a property of thesprayable aqueous compositions for cleaning, sanitizing and disinfectingaccording to the invention. As one skilled in the art understands, bothdynamic (shear) viscosity and bulk viscosity can be used to describecharacteristics of the compositions. The shear viscosity of a liquiddescribes its resistance to shearing flows. The bulk viscosity of aliquid describes its ability to exhibit a form of internal friction thatresists its flow without shear. The measurements of viscosity describedherein use the physical until of poise (P) or centipoise (cPs).

As used herein, the term “ware” refers to items such as eating andcooking utensils, dishes, and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware. Ware also refers to items made ofplastic. Types of plastics that can be cleaned with the compositionsaccording to the invention include but are not limited to, those thatinclude polycarbonate polymers (PC), acrilonitrile-butadiene-styrenepolymers (ABS), and polysulfone polymers (PS). Another exemplary plasticthat can be cleaned using the compounds and compositions of theinvention include polyethylene terephthalate (PET).

As used herein, “weight percent,” “wt.-%,” “percent by weight,” “% byweight,” and variations thereof refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt.-%,” etc.

As used herein, the term “water soluble” refers to a composition or acomponent if it is at least 90 percent soluble in water, at least 95percent soluble in water, at least 98 percent soluble in water, at least99 percent soluble in water, or at least 99.9 percent soluble in water.

The methods and compositions of the present invention may comprise,consist essentially of, or consist of the components and ingredients ofthe present invention as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods and compositions.

Cleaning Compositions

According to the invention, the cleaning compositions comprise of atleast one sanitizer, disinfectant, and/or antimicrobial compound and atleast one polymer compound and provide cleaning activity with a reducedacute toxicity as a result of reduced inhalation risk of thecomposition. The present invention relates to reduced-misting andreduced-inhalation aqueous cleaning compositions comprising, consistingof or consisting essentially of at least one sanitizer, disinfectantand/or antimicrobial compound and at least one polymer compound. In someembodiments, the compositions may be dispensed with a trigger sprayer,such as non-low velocity or a low velocity trigger sprayer. Thecompositions may be dispensed in alternative manners as well. Thecleaning compositions provide ease in manufacturing as a result of therapid dispersion of the polymer into homogenous solutions. The cleaningcompositions provide further benefits in addition to the ease inmanufacturing, including for example, ease in application when usingspray applications due to the reduced viscosity profiles allowing easeof use with spray triggers. Still further, the cleaning compositionsprovide little to no misting of the formulations and increased rate ofcleaning in comparison to compositions comprising conventionalthickeners. Further aspects of reduced misting compositions arediscussed in U.S. patent application Ser. No. 15/602,532, filed May 23,2017, now U.S. Pub. No. 2017/0335254; and U.S. patent application Ser.No. 15/603,039, filed May 23, 2017, now U.S. Pub. No. 2017/0335253, eachof which is incorporated by reference in its entirety.

The cleaning composition may be referred to as a non-Newtonian fluid.Newtonian fluids have a short relaxation time and have a directcorrelation between shear and elongational viscosity (the elongationalviscosity of the fluid equals three times the shear viscosity). Shearviscosity is a measure of a fluid's ability to resist the movement oflayers relative to each other. Elongational viscosity, which is alsoknown as extensional viscosity, is a measure of a fluid's ability tostretch elastically under elongational stress. Non-Newtonian fluids donot have a direct correlation between shear and elongational viscosityand are able to store elastic energy when under strain, givingexponentially more elongational than shear viscosity and producing aneffect of thickening under strain (i.e., shear thickening). Theseproperties of non-Newtonian fluids result in the cleaning compositionthat has a low viscosity when not under shear but that thickens whenunder stress from the trigger sprayer forming larger droplets.

In some embodiments, the cleaning composition has a relatively low shearviscosity when not under strain. In an embodiment, the shear viscosityof the cleaning composition containing the inverse emulsion polymer(s)is comparable to the shear viscosity of water and may be referred to asa “thin liquid”. A suitable shear viscosity for the cleaningcompositions containing a polymer(s) is from about 1 to 1000 cPs,preferably from 1 to 100 cPs. In one example, the anti-mist componentsdo not increase the shear viscosity of the cleaning composition when notunder strain and the increased shear viscosity is created by othercomponents, such as a surfactant. The present invention provides anunexpected benefit in the viscosity of the anti-mist compositions as aresult of the flexible viscoelastic compositions afforded by the inverseemulsion polymers.

In some embodiments, the median particle size of the dispensed solutionof the reduced-misting cleaning compositions is sufficiently large toreduce misting and thereby reduce the inhalation risk associated withhigh misting compositions. As one skilled in the art appreciates,particles having droplet size of less than about 10 microns can bereadily inhaled. Moreover, particles having droplet size of less thanabout 0.1 microns can be readily inhaled into the lungs. Therefore, inmany aspects of the invention the testing and evaluation of the cleaningcompositions according to the invention focus on the reduction ofmisting, in particular reduction or elimination of micron sizes of about10 or less. In an aspect of the invention, a suitable median particlesize is about 11 microns or greater, 50 microns or greater, 70 micronsor greater, about 10 microns or greater, about 150 microns or greater,or about 200 microns or greater. The suitable median particle size maydepend on the composition of the ready to use composition (RTU). Forexample, a suitable median particle size for a strongly alkaline oracidic use solution may be about 100 microns or greater, and moreparticularly about 150 microns or greater, and more particularly about200 microns or greater. A suitable median particle size for a moderatelyalkaline or acidic RTU may be about 11 microns or greater, preferablyabout 50 microns or greater, and more preferably about 150 microns orgreater.

The cleaning compositions according to the invention beneficiallyprovide stable compositions in terms of retained performance of thepolymer, solution stability, and microbial efficacy, wherein the polymerretains stability for at least about one year at ambient temperature ofabout 60° F. to about 80° F., or at least about two years at ambienttemperature of about 60° F. to about 80° F. The stability is measured bythe maintained anti-misting properties of the cleaning compositions.

In an aspect, the cleaning compositions according to the inventioncomprises, consist of, and/or consist essentially of the components asshown in Table 1 wherein the active sanitizer, disinfectant and/orantimicrobial compound employed impacts the selection of the polymerform and charge to provide the unexpected and beneficial effect ofhaving reduced inhalation risk coupled with the sanitizing, disinfectantand/or antimicrobial properties.

TABLE 1 Sanitizer, Disinfectant, and/or Antimicrobial CompoundQuaternary Ammonium Compounds Acid Sanitizers Oxidizers Amines PolymerInverse Inverse Inverse Inverse Form Emulsion, Emulsion, Emulsion,Emulsion, Dispersion, Dispersion, Dispersion, Dispersion, and/or PowderPowder and/or Powder and/or Power and/or Xanthan Gum Xanthan Gum XanthanGum Polymer Cationic, Cationic, Cationic, Cationic, Charge NonionicNonionic, Nonionic, Nonionic, Anionic Anionic Anionic

Cleaning Component

The cleaning compositions according to the invention contain a cleaningcompound which comprises at least one sanitizer, disinfectant, orantimicrobial compound. In an embodiment of the invention, the cleaningcompound is a quaternary ammonium compound, an acid sanitizer, anoxidizer, an amine, or combinations thereof.

Quaternary Ammonium Compounds

According to an embodiment of the invention, the cleaning compositionscomprise at least one quaternary ammonium compound and at least onepolymer compound. Without wishing to be limited to a particular theoryof the invention, the cleaning compositions of the present invention,when utilized at acidic pH, influence the interactions betweenquaternary ammonium compounds and protein. In particular, theutilization of quaternary ammonium compounds at an acidic pH reduceselectrostatic interactions between positively charged quaternaryammonium compounds with negatively or partially negatively chargedbiological matter reduces the risk of toxicity and the inhalation risksassociated with quaternary ammonium compounds. Further, the addition ofthe polymer component causes the composition to resist formulation of anamount of mist or aerosol during storage and application that can causerespiratory distress.

The cleaning compositions according to the invention overcome theconcerns of acute toxicity of quaternary ammonium compounds whileproviding efficacious antimicrobial and/or sanitizing capabilities. Thecompositions of quaternary ammonium compound and acid component reduceacute toxicity. Without seeking to be bound to a particular theory,control of the pH of concentrated compositions containing quaternaryammonium compounds reduces electrostatic interactions between quaternaryammonium compounds and biological matter, specifically duringinhalation. Theoretical surface charge of casein proteins as a functionof pH are summarized in Table 2, to illustrate pH—electrostatic chargerelationship of proteins. i.e., biological matter. As shown in Table 2and as one of ordinary skill in the art would appreciate, as the pHnears the isoelectric point, a protein while demonstrate a net zerocharge.

TABLE 2 Protein Net Theoretical Compatibility with pH Charge CationicSurfactants   0-4.59 Net cationic Positive (MW, charge, molar ratiodependent) 4.6 Net zero Neutral (MW, charge, molar ratio chargedependent) 4.61-12   Net anionic Negative interactions (MW, charge,molar ratio dependent)

At physiological pH of the lungs, about 7.25-7.45, most biologicalmatter has an anionic change. If the biological matter is then lessanionic, i.e., close to/at/or below its respective isoelectric point orpKa, it is believed that according to the theoretical compatibilityshown in Table 2, quaternary ammonium compounds and biological matterhave reduced electrostatic interactions.

In an aspect of the invention where a surfactant is included in thecleaning compositions, cationic surfactants are disfavored due to anincrease in electrostatic interactions, thus increasing the toxicity ofthe compositions.

As such, anionic, nonionic, and amphoteric surfactants, and combinationsthereof are favored in order to decrease interactions between biologicalmatter and quaternary ammonium compounds. Similarly, acid components areselected in order to control pH as well as aid in the decrease ofelectrostatic interactions. Further discussion of quaternary ammoniumcompounds and their suitable for use in an reduced inhalation cleaningcomposition can be found in U.S. patent application Ser. No. 15/445,146,filed Feb. 28, 2017 [attorney docket number PT10767USU1], the entirecontents of which are incorporated herein by reference in its entirety.

The cleaning compositions according to an embodiment of the inventioninclude at least one quaternary ammonium compound. Certain quaternaryammonium compounds are known to have antimicrobial activity.Accordingly, various quaternary ammonium compound with antimicrobialactivity can be used in the composition of the invention. In an aspect,the quaternary ammonium compound is an antimicrobial “quat.” The term“quaternary ammonium compound” or “quat” generally refers to anycomposition with the formula

where R1-R4 are alkyl groups that may be alike or different, substitutedor unsubstituted, saturated or unsaturated, branched or unbranched, andcyclic or acyclic and may contain ether, ester, or amide linkages; theymay be aromatic or substituted aromatic groups. In an aspect, groups R1,R2, R3, and R4 each have less than a C20 chain length. X- is an anioniccounterion. The term “anionic counterion” includes any ion that can forma salt with quaternary ammonium. Examples of suitable counterionsinclude halides such as chlorides and bromides, propionates,methosulphates, saccharinates, ethosulphates, hydroxides, acetates,phosphates, carbonates (such as commercially available as Carboquat H,from Lonza), and nitrates. Preferably, the anionic counterion ischloride.

In some embodiments, quaternary ammoniums having carbon chains of lessthan 20 are included in compositions of the invention. Examples ofquaternary ammonium compounds useful in the present invention includebut are not limited to alkyl dimethyl benzyl ammonium chloride, alkyldimethyl ethylbenzyl ammonium chloride, octyl decyl dimethyl ammoniumchloride, dioctyl dimethyl ammonium chloride, and didecyl dimethylammonium chloride to name a few. A single quaternary ammonium or acombination of more than one quaternary ammonium may be included incompositions of the invention. Further examples of quaternary ammoniumcompounds useful in the present invention include but are not limited tobenzethonium chloride, ethyl benzethonium chloride, myristyl trimethylammonium chloride, methyl benzethonium chloride, cetalkonium chloride,cetrimonium bromide (CTAB), carnitine, dofanium chloride, tetraethylammonium bromide (TEAB), domiphen bromide, benzododecinium bromide,benzoxonium chloride, choline, cocamidopropyl betaine (CAPB), anddenatonium.

In some embodiments, quaternary ammoniums having carbon chains of lessthan 20 or C2-C20 are included in compositions of the invention. Inother embodiments, quaternary ammoniums having carbon chains of C6-C18,C12-C18, C12-C16 and C6-C10 are included in compositions of theinvention. Examples of quaternary ammonium compounds useful in thepresent invention include but are not limited to alkyl dimethyl benzylammonium chloride, alkyl dimethyl ethylbenzyl ammonium chloride, octyldecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride,and didecyl dimethyl ammonium chloride to name a few. A singlequaternary ammonium or a combination of more than one quaternaryammonium may be included in compositions of the invention.

Further examples of quaternary ammonium compounds useful in the presentinvention include but are not limited to benzethonium chloride,ethylbenzyl alkonium chloride, myristyl trimethyl ammonium chloride,methyl benzethonium chloride, cetalkonium chloride, cetrimonium bromide(CTAB), carnitine, dofanium chloride, tetraethyl ammonium bromide(TEAB), domiphen bromide, benzododecinium bromide, benzoxonium chloride,choline, cocamidopropyl betaine (CAPB), denatonium, and mixturesthereof. In an aspect, combinations of quaternary ammonium compounds areparticularly preferred for compositions of the invention, such as forexample the commercially-available products Bardac 205/208M.

In some embodiments depending on the nature of the R group, the anion,and the number of quaternary nitrogen atoms present, the antimicrobialquaternary ammonium compounds may be classified into one of thefollowing categories: monoalkyltrimethyl ammonium salts;monoalkyldimethylbenzyl ammonium salts; dialkyldimethyl ammonium salts;heteroaromatic ammonium salts; polysubstituted quaternary ammoniumsalts; bis-quaternary ammonium salts; and polymeric quaternary ammoniumsalts. Each category will be discussed herein.

Monoalkyltrimethyl ammonium salts contain one R group that is along-chain alkyl group, and the remaining R groups are short-chain alkylgroups, such as methyl or ethyl groups. Some non-limiting examples ofmonoalkyltrimethyl ammonium salts include cetyltrimethylammoniumbromide, commercial available under the tradenames Rhodaquat M242C/29and Dehyquart A; alkyltrimethyl ammonium chloride, commerciallyavailable as Arquad 16; alkylaryltrimethyl ammonium chloride; andcetyldimethyl ethylammonium bromide, commercially available as AmmonyxDME.

Monoalkyldimethylbenzyl ammonium salts contain one R group that is along-chain alkyl group, a second R group that is a benzyl radical, andthe two remaining R groups are short-chain alkyl groups, such as methylor ethyl groups. Monoalkyldimethylbenzyl ammonium salts are generallycompatible with nonionic surfactants, detergent builders, perfumes, andother ingredients. Some non-limiting examples of monoalkyldimethylbenzylammonium salts include alkyldimethylbenzyl ammonium chlorides,commercially available as Barquat from Lonza Inc.; and benzethoniumchloride, commercially available as Lonzagard, from Lonza Inc.Additionally, the monoalkyldimethylbenzyl ammonium salts may besubstituted. Non-limiting examples of such salts includedodecyldimethyl-3,4-dichlorobenzyl ammonium chloride. Finally, there aremixtures of alkyldimethylbenzyl and alkyldimethyl substituted benzyl(ethylbenzyl) ammonium chlorides commercially available as BTC 2125Mfrom Stepan Company, and Barquat 4250 from Lonza Inc.

Dialkyldimethyl ammonium salts contain two R groups that are long-chainalkyl groups, and the remaining R groups are short-chain alkyl groups,such as methyl groups. Some non-limiting examples of dialkyldimethylammonium salts include didecyldimethyl ammonium halides, commerciallyavailable as Bardac 22 from Lonza Inc.; didecyl dimethyl ammoniumchloride commercially available as Bardac 2250 from Lonza Inc.; dioctyldimethyl ammonium chloride, commercially available as Bardac LF andBardac LF-80 from Lonza Inc.); and octyl decyl dimethyl ammoniumchloride sold as a mixture with didecyl and dioctyl dimethyl ammoniumchlorides, commercially available as Bardac2050 and 2080 from Lonza Inc.

Heteroaromatic ammonium salts contain one R group that is a long-chainalkyl group, and the remaining R groups are provided by some aromaticsystem. Accordingly, the quaternary nitrogen to which the R groups areattached is part of an aromatic system such as pyridine, quinoline, orisoquinoline. Some non-limiting examples of heteroaromatic ammoniumsalts include cetylpyridinium halide, commercially available as Sumquat6060/CPC from Zeeland Chemical Inc.;1-[3-chloroalkyl]-3,5,7-triaza-1-azoniaadamantane, commerciallyavailable as Dowicil 200 from The Dow Chemical Company; andalkyl-isoquinolinium bromide.

Polysubstituted quaternary ammonium salts are a monoalkyltrimethylammonium salt, monoalkyldimethylbenzyl ammonium salt, dialkyldimethylammonium salt, or heteroaromatic ammonium salt wherein the anion portionof the molecule is a large, high-molecular weight (MW) organic ion. Somenon-limiting examples of polysubstituted quaternary ammonium saltsinclude alkyldimethyl benzyl ammonium saccharinate, anddimethylethylbenzyl ammonium cyclohexylsulfamate.

Bis-quaternary ammonium salts contain two symmetric quaternary ammoniummoieties having the general formula:

Where the R groups may be long or short chain alkyl, a benzyl radical orprovided by an aromatic system. Z is a carbon-hydrogen chain attached toeach quaternary nitrogen. Some non-limiting examples of bis-quaternaryammonium salts include 1,10-bis(2-methyl-4-aminoquinoliniumchloride)-decane; and 1,6-bis[1-methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethylammonium chloride] hexane or triclobisoniumchloride.

In an aspect, the quaternary ammonium compound is a medium to long chainalkyl R group, such as from 8 carbons to about 20 carbons, from 8carbons to about 18 carbons, from about 10 to about 18 carbons, and fromabout 12 to about 16 carbons, and providing a soluble and goodantimicrobial agent.

In an aspect, the quaternary ammonium compound is a short di-alkyl chainquaternary ammonium compound having an R group, such as from 2 carbonsto about 12 carbons, from 3 carbons to about 12 carbons, or from 6carbons to about 12 carbons.

In a preferred aspect, the quaternary ammonium compound is an alkylbenzyl ammonium chloride, a dialkyl benzyl ammonium chloride, a blend ofalkyl benzyl ammonium chloride and dialkyl benzyl ammonium chloride,didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride,a blend of didecyl dimethyl ammonium chloride and dioctyl dimethylammonium chloride, or mixtures thereof. In a preferred embodiment, thequaternary ammonium compound used in the cleaning compositions of theinvention is comprised of a mixture of dialkyl quaternary ammonium andalkyl benzyl quaternary ammonium.

According to embodiments of the invention providing cleaningcompositions, an effective amount of the quaternary ammonium compound isprovided in combination with a polymer to provide antimicrobial efficacyagainst a broad spectrum of microbes, including gram negative microbessuch as E. coli. Suitable concentrations of the quaternary ammoniumcompound in such a use solution include at least about 10 ppm, at leastabout 50 ppm, or at least about 100 ppm, or at least about 150 ppm, orat least about 200 ppm, or at least about 250 ppm, or at least about 300ppm, or from about 100-500 ppm, or from about 100-300 ppm, or any rangestherein. In some aspects, the activated microbial compositions accordingto the invention provide efficacy against gram negative conventionallyrequirement more than 150 ppm quaternary ammonium compounds for anyantimicrobial efficacy at concentrations below about 150 ppm, or belowabout 100 ppm according to the synergy in combination with the anionicsurfactants and/or acids. Without being limited according to theinvention, all ranges recited are inclusive of the numbers defining therange and include each integer within the defined range.

Additional suitable concentrations of the quaternary ammonium compoundin a use solution for the cleaning compositions include between about 1ppm and about 10,000 ppm, 1 ppm and about 1,000 ppm, 5 ppm and about 400ppm, 10 ppm and about 400 ppm, 20 ppm and about 400 ppm, 25 ppm andabout 400 ppm, 50 ppm and about 400 ppm, 75 ppm and about 400 ppm, or100 ppm and about 400 ppm. Additional suitable concentrations of thequaternary ammonium compound in a use solution for the cleaningcompositions include between about 0.0001 wt.-% to about 10 wt.-%, about0.001 wt.-% and about 10 wt.-%, about 0.01 wt.-% and about 10 wt.-%,about 1.0 wt.-% to and about 10 wt.-%. Without being limited accordingto the invention, all ranges recited are inclusive of the numbersdefining the range and include each integer within the defined range.

Acid Sanitizers

Various acid sanitizers can be employed according to the invention. Inembodiments of the invention, the acid sanitizer may be a carboxylicacid, peracid, mineral acid, organic acid, amino acid, fatty acid,linear alkylbenzene. It is to be understood that derivatives of each andcombinations of acid sanitizers may be employed by the presentinvention.

In an aspect of the invention, the acid sanitizer is a carboxylic acid.Generally, carboxylic acids have the formula R—COOH wherein the R mayrepresent any number of different groups including aliphatic groups,alicyclic groups, aromatic groups, heterocyclic groups, all of which maybe saturated or unsaturated as well as substituted or unsubstituted.Carboxylic acids also occur having one, two, three, or more carboxylgroups. Carboxylic acids have a tendency to acidify aqueous compositionsin which they are present as the hydrogen atom of the carboxyl group isactive and may appear as an anion. The carboxylic acid constituentwithin the present composition when combined with aqueous hydrogenperoxide generally functions as an antimicrobial agent as a result ofthe presence of the active hydrogen atom. Moreover, the carboxylic acidconstituent within the invention maintains the composition at an acidicpH. Examples of such carboxylic acids include, but are not limited to,acetic acid, citric acid, succinic acid, adipic acid, hydroxyaceticacid, and lactic acid. One of skill in the art will appreciate thatother carboxylic acids may be used for purposes of the invention.

A variety of C6-C18 peroxyacids may be employed in the composition ofthe invention such as peroxyfatty acids, monoperoxy- ordiperoxydicarboxylic acids, and peroxyaromatic acids. The C6-C18peroxyacids employed in the present invention may be structurallyrepresented as follows: R1 —CO3 H, wherein R1 is a hydrocarbon moietyhaving from about 5 to 17 carbon atoms (a C18 peroxyacid is generallyrepresented structurally as C7 —CO3 H). R1 may have substituents in thechain, e.g., —OH, CO2 H, or heteroatoms (e.g., —O—as in alkylethercarboxylic acids), as long as the antimicrobial properties of theoverall composition are not significantly affected. It should berecognized that “R1” substituents or heteroatoms may change the overallacidity (i.e., pKa) of the carboxylic acids herein described. Suchmodification is within the contemplation of the present inventionprovided the advantageous antimicrobial performance is maintained.Furthermore, R1 may be linear, branched, cyclic or aromatic. Preferredhydrocarbon moieties (i.e. preferred R1's) include linear, saturated,hydrocarbon aliphatic moieties having from 7 to 11 carbon atoms (or 8 to12 carbon atoms per molecule).

Specific examples of suitable C6-C18 carboxylic fatty acids which can bereacted with hydrogen peroxide to form peroxyfatty acids include suchsaturated fatty acids as hexanoic (C6), enanthic (heptanoic) (C7),caprylic (octanoic) (C8), pelargonic (nonanoic) (C9), capric (decanoic)(C10), undecyclic (undecanoic) (C11), lauric (dodecanoic) (C12),trideclic (tridecanoic) (C13), myristic (tetradecanoic) (C14), palmitic(hexadecanoic) (C16), and stearic (octodecanoic) (C18). These acids canbe derived from both natural and synthetic sources. Natural sourcesinclude animal and vegetable fats or oils which should be fullyhydrogenated. Synthetic acids can be produced by the oxidation ofpetroleum wax. Particularly preferred peroxyfatty acids for use in thecomposition of the invention are linear monoperoxy aliphatic fatty acidssuch as peroxyoctanoic acid, peroxydecanoic acid, or mixtures thereof.

Other suitable C6-C18 peroxyacids are derived from the oxidation ofdicarboxylic acids and aromatic acids. Suitable dicarboxylic acidsinclude adipic acid (C6) and sebacic acid (C10). An example of asuitable aromatic acid is benzoic acid. These acids can be reacted withhydrogen peroxide to form the peracid form suitable for use in thecomposition of the invention. Preferred peracids in this group includemonoperoxy- or diperoxyadipic acid, monoperoxy- or diperoxysebacic acid,and peroxybenzoic acid.

The above peroxyacids provide antibacterial activity against a widevariety of microorganisms, such as gram positive (e.g., Staphylococcusaureus) and gram negative (e.g., Escherichia coli) microorganisms,yeast, molds, bacterial spores, etc. When the above C6-C18 peroxyacidsare combined with a C1-C4 peroxycarboxylic acid, greatly enhancedactivity is shown compared to the C1-C4 peroxycarboxylic acid alone orthe C6-C18 peroxyacid alone. The C1-C4 peroxycarboxylic acid componentcan be derived from a C1-C4 carboxylic acid or dicarboxylic acid byreacting the acid with hydrogen peroxide. Examples of suitable C1-C4carboxylic acids include acetic acid, propionic acid, glycolic acid, andsuccinic acid. Preferable C1-C4 peroxycarboxylic acids for use in thecomposition of the invention include peroxyacetic acid, peroxypropionicacid, peroxyglycolic acid, peroxysuccinic acid, or mixtures thereof.

The peracid components used in the composition of the invention can beproduced in a simple manner by mixing a hydrogen peroxide (H2O2)solution with the desired amount of acid. With the higher molecularweight fatty acids, a hydrotrope coupler may be required to helpsolubilize the fatty acid. The H2O2 solution also can be added topreviously made peracids such as peracetic acid or various perfattyacids to produce the peracid composition of the invention. Theconcentrate can contain about 1 to 50 wt. %, preferably about 5 to 25wt. % of hydrogen peroxide. U.S. Pat. No. 5,200,189, filed Jul. 31, 1991further discloses the use of peracids in cleaning compositions and ishereby incorporated by reference in its entirety.

In an aspect of the invention, the acid sanitizer is a mineral acid,i.e., an inorganic acid. Examples of such mineral acids include, but arenot limited to, phosphoric acid, sulfamic acid, sulfuric acid, nitricacid, and hydrocholoric acid. Generally, all mineral acids form hydrogenions and the conjugate base ions when dissolved in water. For example,sulfuric acid forms hydrogen sulfate in aqueous solutions via completeionization to form hydronium ions and hydrogen sulfate. Such conjugatebases are also useful acid components for purposes of the invention.

In an aspect of the invention, the acid sanitizer is an organic acid.Suitable organic acids include, but are not limited to, methane sulfonicacid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid,xylene sulfonic acid, cumene sulfonic acid, benzene sulfonic acid,formic acid, acetic acid, mono, di, or tri-halocarboyxlic acids,picolinic acid, dipicolinic acid, and mixtures thereof.

In an aspect of the invention, the acid sanitizer is an amino acidand/or an amino acid derivative. Generally, an amino acid contains anamine functional group and a carboxylic acid functional group, usuallyalong with a side chain group to each amino acid. Suitable amino acidand/or amino acid derivatives include, but are not limited to alanine,arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine,glycine, histidine, isoleucine, leucine, lysine, methionine,phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine,selenocysteine, pyrrolysine, and derivatives thereof.

In an aspect of the invention, the acid sanitizer is a fatty acid and/orfatty acid surfactant. Antimicrobially active acids have been used insanitizing operations. For instance, U.S. Pat. No 404,040 describes asanitizing composition comprising aliphatic, short chain fatty acids, ahydrotrope or solubilizer for the fatty acids, and ahydrotrope-compatible acid, and U.S. Pat. No. 5,330,769 describes fattyacid sanitizer concentrates and diluted final solutions which includeindividual amounts of germicidally effective fatty acid, hydrotrope, astrong acid group consisting of phosphoric acid and sulfuric acid ormixtures thereof sufficient to lower the pH of the final solutions toabout 1-5, and a concentrate stabilizing weak acid component selectedfrom the group consisting of propionic, butyric and valeric acids andmixtures thereof. As used herein, the term “fatty acid” includes any ofa group of carboxylic acids that include an alkyl chain. In someembodiments, the alkyl groups can be linear or branched, and saturatedor unsaturated. The chain of alkyl groups contains any length of carbonatoms. In some embodiments, the chain of alkyl groups contains from 4 to12 carbon atoms, 5 to 11 carbon atoms, or 8 to 10 carbon atoms.Exemplary fatty acids can be selected from hexanoic acid, heptanoicacid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, palmiticacid, stearic acid, oleic acid, caproic acid, caprylic acid, capric acidand mixtures thereof. Exemplary longer alkyl chain fatty acids can beselected from for example myristic acid, arachidic acid, behenic acid,lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid,sapienic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidicacid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucicacid, decosahexaenoic acid, gadoleic acid, erucic acid, margaric acid,behenic acid, ricinoleic acid, lignoceric acid, licanic acid,eleostearic acid and mixtures thereof.

In an aspect of the invention, the acid sanitizer is a linearalkylbenzene. Suitable linear alkylbenzenes include linear alkylbenzenesulfonate (LAS) and Linear alkylbenzene sulfonic acid (LABSA). Otherswhich can be employed are alkyl benzene sulfonates, alkyl sulfonates,alkyl ether sulfates, alpha olefin sulfonates, alkyl sarcosinates, andmixtures thereof.

Oxidizers

According to an embodiment of the invention, the cleaning compositionscomprise at least one oxidizer and at least one polymer compound. Theoxidizer can be any oxidizer that is compatible with a cationic,nonionic, and/or anionic polymers. Examples of such oxidizers includenonorganic oxidizing substances such as, hydrogen peroxide, sodiumpercarbonate, sodium periodate, sodium persulfate, ammonium persulfate,sodium perborate, sodium peroxide, calcium peroxide, silver (II) oxide,ozone, and chlorine dioxide. The oxidizers also include organicoxidizing substance for example, diacyl peroxides, such as benzoylperoxide, ketone peroxides, such as 2,4-pertanedione peroxide,peroxydicarbonates, such as diisopropyl peroxydicarbonate, peroxyesters,such as t-butylperoxy maleic acid, dialkyl peroxides, such as dicumylperoxide, hydroperoxyides, such as t-butyl hydroperoxide, andperoxyketals, such as 2,2-di(t-butyl peroxy) butane. Additionaloxidizers are disclosed in U.S. Pat. No. 5,616,616, filed Jun. 1, 1994and is hereby incorporated by reference in its entirety.

Amines

The cleaning component may also be an antimicrobial amine. The amine maybe a primary, secondary, or tertiary amine. Alternatively, thecomposition can include a quaternary ammonium compound. The amineconcentration in the system can range from about 0.5 to about 8.5 wt. %,about 1.0 to about 3.0 wt. %, or about 1.25 to about 2.0 wt. %. Theamine is preferably a tertiary amine. But, other exemplary antimicrobialamines are: aliphatic amines; aliphatic amine salts such as: aliphaticammonium salts; ether amines such as: those commercially available fromTomah Products as PA-19, PA-1618, PA-1816, DA-18, DA-19, DA-1618,DA-1816; or ether amines with the formulas R₁—O—R₂—NH₂,R₁—O—R₂—NH—R₃—NH₂, or mixtures thereof, where (independently): R₁=alinear saturated or unsaturated C6-C18 alkyl, R₂=a linear or branchedC1-C8 alkyl, and R₃=a linear or branched C1-C8 alkyl, or R₁=a linearC12-C16 alkyl, R₂=a C2-C6 linear or branched alkyl; and R₃=a C2-C6linear or branched alkyl, or R₁=a linear alkyl C12-C16, or a mixture oflinear alkyl C10-C12 and C14-C16 R₂=C3, and R₃=C3; ether amine saltssuch as: ether ammonium salts; diamines such as: N-coco-1,3-propylenediamine (such as Duomeen®—Akzo Chemie America, Armak Chemicals);N-oleyl-1,3-propylene diamine (such as Duomeen®—Akzo Chemie America,Armak Chemicals); N-tallow-1,3-propylene diamine (such as Duomeen®—AkzoChemie America, Armak Chemicals); diamine salts such as: diamine acetate(or other counterion), or diamine sales with the formulas[(R₁)NH(R₂)NH₃]⁺(CH₃COO)⁻ or [(R₁)NH₂(R₂)NH₃ ⁺]⁺(CH₃COO)₂— where: R₁=aC10-C18 aliphatic group or an ether group having the formula R₁₀OR₁₁where R₁₀=a C10-C18 aliphatic group and R₁₁=a C1-C5 alkyl group; andR₂=a C1-C5 alkylene group, or R₁=a C10-C18 aliphatic group derived froma fatty acid, and R₂=propylene. Further suitable amines are disclosed inU.S. Pat. No. 7,964,548, filed Apr. 5, 2010 and is hereby incorporatedby reference in its entirety.

Polymer Component

The cleaning compositions according to the invention include a polymercomponent. As shown in Table 1, the selection of the cleaning componentinfluences the desired charge of the polymer in order to achieve thedesired reduced inhalation risk while beneficially providing thecleaning, sanitizing, disinfecting and/or antimicrobial efficacy. In anaspect of the invention, the polymer may have a cationic, nonionic, oranionic charge and may come in the form of an inverse emulsion polymer,dispersion polymer, powder polymer, and/or xanthan gum.

Inverse Emulsion Polymer

The cleaning compositions according to an embodiment of the inventioninclude an inverse emulsion polymer. In an aspect, the inverse emulsionpolymer is a water-soluble modified polymer. In an aspect, the inverseemulsion polymer may be cationic, anionic, nonionic, amphoteric and/orassociative. The terms emulsion polymer and latex polymer may be usedinterchangeably herein, referring to a water-in-oil (W/O) emulsionpolymer comprising a cationic, anionic, nonionic, and/or zwitterionicpolymer.

In an aspect, the inverse emulsion polymer has a high molecular weightof from about 3,000 Da to about 50 million Da, from about 500,000 Da toabout 30 million Da, from about 1 million Da to about 25 million Da, andpreferably from about 3 million Da to about 20 million Da.

In an aspect, the inverse emulsion polymer has an intrinsic viscosityabove about 1, more preferably above about 6 and still more preferablyfrom about 15 to about 30 dl/g. The reduced specific viscosity of theinverse emulsion polymer is generally above 3, preferably above about 8and frequently above about 24 dl/g.

In an aspect, the inverse emulsion polymers according to the inventionhave a particle size ranging from about 0.1 to about 10 microns,preferably from about 0.25 to about 3 microns.

In an aspect, the inverse emulsion polymers according to the inventionhave a bulk viscosity of ranging from about 50 — 5000 cPs, andpreferably from about 100 — 2000 cPs.

The inverse emulsion polymers according to the invention are stabilizeddispersions of flexible polymer chains containing aqueous droplets in aninert hydrophobic phase. In an aspect, the inverse emulsion polymers arecomprised of three components including (1) a hydrophobic or hydrocarboncontinuous oil phase, (2) an aqueous phase, and (3) a water-in-oilemulsifying agent (i.e. surfactant system). In an aspect, the inverseemulsion polymers are hydrocarbon continuous with the water-solublepolymers dispersed within the hydrocarbon matrix. The inverse emulsionpolymers are then “inverted” or activated for use by releasing thepolymer from the particles using shear, dilution, and, generally,another surfactant. See U.S. Pat. No. 3,734,873 which is incorporatedherein by reference. Representative preparations of high molecularweight inverse emulsion polymers are described in U. S. Pat. Nos.2,982,749; 3,284,393, and 3,734,873, each of which are incorporatedherein by reference.

In another aspect, an inverse emulsion polymer is formed through thepolymerization of an aqueous solution of monomers under free radicalpolymerization conditions to form a polymer solution, as disclosed inU.S. Pat. Nos. 6,605,674 and 6,753,388, each of which are incorporatedherein by reference. In a preferred aspect, the inverse emulsion polymeris obtained by polymerizing an aqueous solution of ethylenicallyunsaturated water-soluble or water-dispersible monomers and/orcomonomers emulsified in a hydrophobic continuous phase by using oil-and/or water soluble initiators via radical polymerization.

As used herein, the term “monomer” for an inverse emulsion polymer meansa polymerizable allylic, vinylic or acrylic compound. The monomer may beanionic, cationic, nonionic and/or zwitterionic. In some embodimentsvinyl monomers are preferred, and in other embodiments acrylic and/oracrylamide monomers, such as acrylic acid or its salts, N-t-butylacrylamide sulfonic acid (ATBS) or its salts, acrylamide tertiary butylsulfonic acid or its salts, and2-(acryloyloxy)-N,N,N-trimethylethananminium (DMAEA.MCQ), are morepreferred. In an embodiment, nonionic monomers are particularly suitablefor use in neutral, acidic, alkaline and/or oxidizing cleaningcompositions. Representative nonionic, water-soluble monomers includeacrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide,N-vinylmethylacetamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate,hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, N-tert-butylacrylamide, N-methylolacrylamide, and thelike.

In an embodiment, anionic monomers are particularly suitable for use inalkaline, neutral and/or oxidizing cleaning compositions. Representativeanionic monomers include acrylic acid, and its salts, including, but notlimited to sodium acrylate, and ammonium acrylate, methacrylic acid, andits salts, including, but not limited to sodium methacrylate, andammonium methacrylate, 2-acrylamido-2-methylpropanesulfonic acid (ATBS),the sodium salt of ATBS, acrylamide tertiary butyl sulfonic acid or itssalts, sodium vinyl sulfonate, styrene sulfonate, maleic acid, and itssalts, including, but not limited to the sodium salt, and ammonium salt,sulfonate itaconate, sulfopropyl acrylate or methacrylate or otherwater-soluble forms of these or other polymerizable carboxylic orsulphonic acids. Sulfomethylated acrylamide, allyl sulfonate, sodiumvinyl sulfonate, itaconic acid, acrylamidomethylbutanoic acid, fumaricacid, vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid,sulfomethylated acrylamide, phosphonomethylated acrylamide, and thelike.

In an embodiment, cationic monomers are particularly suitable for use inacidic and/or oxidizing cleaning compositions. Representative cationicmonomers include dialkylaminoalkyl acrylates and methacrylates and theirquaternary or acid salts, including, but not limited to,dimethylaminoethyl acrylate methyl chloride quaternary salt,dimethylaminoethyl acrylate methyl sulfate quaternary salt,dimethylaminoethyl acrylate benzyl chloride quaternary salt,dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethylacrylate hydrochloric acid salt, dimethylaminoethyl methacrylate methylchloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfatequaternary salt, dimethylaminoethyl methacrylate benzyl chloridequaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt,dimethylaminoethyl methacrylate hydrochloric acid salt,dialkylaminoalkylacrylamides or methacrylamides and their quaternary oracid salts such as acrylamidopropyltrimethylammonium chloride,dimethylaminoethyl acrylate methyl chloride quaternary salt,dimethylaminoethyl acrylate benzyl chloride quaternary salt,dimethylaminoethyl methacrylate methyl chloride quaternary salt,dimethylaminoethyl methacrylate benzyl chloride quaternary salt,methacrylarnidopropyl trimethylammonium chloride, dimethylaminopropylacrylamide methyl sulfate quaternary salt, dimethylaminopropylacrylamide sulfuric acid salt, dimethylaminopropyl acrylamidehydrochloric acid salt, methacrylamidopropyltrimethylammonium chloride,dimethylaminopropyl methacrylamide methyl sulfate quaternary salt,dimethylaminopropyl methacrylamide sulfuric acid salt,dimethylaminopropyl methacrylamide hydrochloric acid salt,diethylaminoethylacrylate, diethylaminoethylmethacrylate,diallyldiethylammonium chloride, diallyldimethylammonium chloride, andthe like.

In an embodiment, zwitterionic monomers are particularly suitable foruse in neutral, acidic, alkaline and/or oxidizing cleaning compositions.Representative zwitterionic monomers includeN,N-dimethyl-N-acryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine,N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine,N,N-dimethyl-N-acrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine,N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine,2-(methylthio)ethyl methacryloyl-S-(sulfopropyl)-sulfonium betaine,2-[(2-acryloylethyl)dimethylammonio]ethyl 2-methyl phosphate,2-(acryloyloxyethyl)-2′-(trimethylammonium)ethyl phosphate,[(2-acryloylethyl)dimethylammonio]methyl phosphonic acid,2-methacryloyloxyethyl phosphorylcholine (MPC),2-[(3-acrylamidopropyl)dimethylammonio]ethyl 2′-isopropyl phosphate(AAPI), 1-vinyl-3-(3-sulfopropyl)imidazolium hydroxide,(2-acryloxyethyl) carboxymethyl methylsulfonium chloride,1-(3-sulfopropyl)-2-vinylpyridinium betaine,N-(4-sulfobutyl)-N-methyl-N, N-diallylamine ammonium betaine (MDABS),N,N-diallyl-N-methyl-N-(2-sulfoethyl)ammonium betaine, and the like.

In an aspect, the aqueous phase is prepared by mixing together in waterone or more water-soluble monomers, and any polymerization additivessuch as inorganic or hydrophobic salts, chelants, pH buffers, processingaids, and the like. In an embodiment, the monomers are ethylenicallyunsaturated water-soluble or water-dispersible monomers and/orcomonomers. In a further embodiment, the monomers are emulsified in ahydrophobic or hydrocarbon continuous oil phase by using oil- and/orwater soluble initiators via radical polymerization, wherein thepolymers may be nonionic, anionic, cationic, and/or zwitterionic. In apreferred embodiment, the monomers are selected from acrylamide ormethacrylamide, such as acrylic acid or its salts, N-t-butyl acrylamidesulfonic acid (ATBS) or its salts, acrylamide tertiary butyl sulfonicacid or its salts, or 2-(acryloyloxy)-N,N,N-trimethylethananminium(DMAEA.MCQ). In a further preferred embodiment, the monomers are furtherselected from the group consisting of diallyldimethylammonium chloride,dimethylaminoethyl acrylate methyl chloride quaternary salt,acrylamidopropyltrimethylammonium chloride, dimethylaminoethylmethacrylate methyl chloride quaternary salt,methacrylamidopropyltrimethylammonium chloride, acrylic acid, sodiumacrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, andammonium methacrylate.

In a preferred embodiment, the monomers are acrylamide anddiallyldimethylammonium chloride. In a further preferred embodiment, themonomers are acrylamide and dimethylaminoethylacrylate methyl chloridequaternary salt. In a further preferred embodiment, the monomers areacrylamide, dimethylaminoethylacrylate benzyl chloride quaternary saltand dimethylaminoethylacrylate methyl chloride quaternary salt.Representative copolymers of acrylic acid and acrylamide useful asmicroparticles include Nalco® 8677 PLUS, available from Nalco ChemicalCompany, Naperville, Ill., USA. Other copolymers of acrylic acid andacrylamide are described in U.S. Pat. No. 5,098,520, incorporated hereinby reference.

The degree of polymerization of monomers in the aqueous phase isdetermined by the change in the reaction density for water-in-oilemulsion polymerization, calorimeterically by measuring the heat ofreaction, by quantitative infrared spectroscopy, or chromatographically,by measuring the level of unreacted monomer.

In an aspect, the aqueous phase is added to the oil phase (under highshear mixing or vigorous stirring) to form an emulsion.

The hydrophobic/hydrocarbon (or oil) phase is prepared by mixingtogether an inert hydrocarbon liquid with one or more oil solublesurfactants. The hydrophobic liquid is selected from the groupconsisting of benzene, xylene, toluene, mineral oils, kerosene, napthas,petroleums and combinations of the same. In a preferred aspect, thehydrophobic liquid is an isoparafinic hydrocarbon. The surfactantmixture should have a low HLB, to ensure the formation of an oilcontinuous emulsion. Appropriate surfactants for water-in-oil emulsionpolymerizations, which are commercially available, are compiled in theNorth American Edition of McCutcheon's Emulsifiers & Detergents, whichis incorporated by reference in its entirety.

In an aspect, the inverse emulsion polymer is a free-flowing liquid. Anaqueous solution of the inverse emulsion polymer, in simplestmethodology, can be generated by adding a desired amount of the emulsionpolymer to water with vigorous mixing in the presence of a high-HLBsurfactant as described in U.S. Pat. No. 3,734,873 which is hereinincorporated by reference in its entirety.

An effective amount of the inverse emulsion polymer is provided to thecleaning compositions to provide ready-to-use reduced inhalation riskcompositions having lower concentrations that conventionalviscosity-modifying polymers. Beneficially, the inverse emulsionpolymers are highly concentrated for dilution systems while maintainingviscoelasticity even for such highly concentrated formulations. Suitableconcentrations of the inverse emulsion polymer in a concentratedformulation include between about 0.0001% and about 1% by weight,between about 0.0005% and about 0.5% by weight, between about 0.01% andabout 0.2% by weight, and more preferably between about 5 ppm and 200ppm active inverse emulsion polymer. Without being limited according tothe invention, all ranges recited are inclusive of the numbers definingthe range and include each integer within the defined range.

Dispersion Polymer

In an embodiment of the invention, the polymer component is a dispersionpolymer. A dispersion polymer means a dispersion of fine particles ofpolymer in an aqueous salt solution, which is prepared by polymerizingmonomers with stirring in an aqueous salt solution in which theresulting polymer is insoluble. See U.S. Pat. Nos. 8, 992,688;5,708,071; 4,929,655; 5,006,590; 5,597,859; 5,597,858 and EuropeanPatent nos. 657,478 and 630,909. In a typical procedure for preparingsolution and gel polymers, an aqueous solution containing one or morewater-soluble monomers and any additional polymerization additives suchas chelants, pH buffers, and the like, is prepared. This mixture ischarged to a reactor equipped with a mixer, a thermocouple, a nitrogenpurging tube and a water condenser. The solution is mixed vigorously,heated to the desired temperature, and then one or more polymerizationinitiators are added. The solution is purged with nitrogen whilemaintaining temperature and mixing for several hours. Typically, theviscosity of the solution increases during this period. After thepolymerization is complete, the reactor contents are cooled to roomtemperature and then transferred to storage. Solution and gel polymerviscosities vary widely, and are dependent upon the concentration andmolecular weight of the active polymer component.

In an aspect of the invention, the dispersion polymer is a cationic,anionic or nonionic high molecular weight dispersion polymer.

Suitable concentrations of the dispersion polymer in a concentratedformulation include between about 0.0001% and about 1% by weight,between about 0.0005% and about 0.5% by weight, between about 0.01% andabout 0.2% by weight, and more preferably between about 5 ppm and 200ppm active dispersion polymer. Without being limited according to theinvention, all ranges recited are inclusive of the numbers defining therange and include each integer within the defined range.

Powder Polymer

In an embodiment of the invention, the polymer component is formulatedas a dried or powder polymer. In one example, the polymer componentincludes a mixture of polyethylene oxide (PEO), polyacrylamide, andpolyacrylate. In a further example, the polymer component includesmixtures of PEO and polyacrylamide. PEO is a high molecular weightpolymer. A suitable PEO can have a molecular weight between about3,000,000 and about 7,000,000. One commercially available PEO is PolyoxWSR 301, which has a molecular weight of about 4,000,000 and isavailable from Dow. A suitable concentration range for PEO is betweenapproximately 0.01 wt.-% and 0.3 wt.-% of the concentrate cleaningsolution. A particular suitable concentrate range for PEO is betweenapproximately 0.01 wt.-% and 0.2 wt.-% of the concentrate cleaningsolution. The polymer component may alternatively or additionallyinclude a polyacrylamide. A suitable polyacrylamide can have a molecularweight between about 8 million and 16 million, and more suitably betweenabout 11 million and 13 million. One commercially availablepolyacrylamide is SuperFloc® N-300 available from Kemira WaterSolutions, Inc. A suitable concentration range for polyacrylamide isbetween approximately 0.01 wt.-% and 0.3 wt.-% of the concentratecleaning solution. A particularly suitable concentration range forpolyacrylamide is approximately 0.01 wt.-% and 0.2 wt.-% of theconcentrate cleaning solution.

Polyacrylate is a high molecular weight polymer. A suitable polyacrylatepolymer can have a molecular weight between about 500,000 and about 3million. A more suitable polyacrylate polymer can have a molecularweight of at least about 1 million. One commercially availablepolyacrylate is Aquatreat® AR-7H available from Akzo Nobel. Suitablepolyacrylate concentrations in the concentrate composition are betweenabout 0.5 wt.-% to about 20 wt.-%. Particularly suitable polyacrylateconcentrations in the concentrate composition are between about 1 wt.-%and about 10 wt.-%.

In a further embodiment of the invention, other known suitable polymersmay be formulated as dried polymer, or powders for inclusion in thecleaning compositions according to the invention. Examples of suchsuitable polymers can be found in U.S. Pat. Nos. 9,127,241 and9,206,281, which are incorporated by reference in their entirety.

Xanthan Gum

In an aspect of the invention, the polymer component is xanthan gum.Xanthan is an extracellular polysaccharide of xanthomonas campestras.Xanthan is made by fermentation based on corn sugar or other cornsweetener by-products. Xanthan comprises a polybeta-(1→4)-D-Glucopyranosyl backbone chain, similar to that found incellulose. Aqueous dispersions of xanthan gum and its derivativesexhibit novel and remarkable rheological properties. Low concentrationsof the gum have relatively high viscosity which permit it economical useand application. Xanthan gum solutions exhibit high pseudoplasticity,i.e. over a wide range of concentrations, rapid shear thinning occursthat is generally understood to be instantaneously reversible.Non-sheared materials have viscosity that appears to be independent ofthe pH and independent of temperature over wide ranges. Preferredxanthan materials include crosslinked xanthan materials. Xanthanpolymers can be crosslinked with a variety of known covalent reactingcrosslinking agents reactive with the hydroxyl functionality of largepolysaccharide molecules and can also be crosslinked using divalent,trivalent or polyvalent metal ions. Such crosslinked xanthan gels aredisclosed in U.S. Pat. No. 4,782,901, which patent is incorporated byreference herein. Suitable crosslinking agents for xanthan materialsinclude metal cations such as Al+3, Fe+3, Sb+3, Zr+4 and othertransition metals, etc. Known organic crosslinking agents can also beused. The preferred crosslinked xanthan agent of the invention is

KELZAN AR, a product of Kelco, a division of Merck Incorporated. KELZANAR is a crosslinked xanthan that provides a thixotropic cleaner that canproduce large particle size mist or aerosol when sprayed.

Suitable concentrations of the xanthan gum in a concentrated solutioninclude between about 0.0001% and about 1% by weight, between about0.0005% and about 0.5% by weight, between about 0.01% and about 0.2% byweight, and more preferably between about 5 ppm and 200 ppm xanthan gum.Without being limited according to the invention, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range.

Acid Component

The cleaning compositions according to the invention optionally includeat least one acid component. In other aspects, the cleaning compositionsinclude at least two acid components. The cleaning compositionsaccording to the invention optionally include at least one acidcomponent when the cleaning component is a quaternary ammonium compound.Without seeking to be limited to particular theory of the invention, itis believed that the inclusion of an acid component maintains the pH ofthe cleaning compositions at an acidic pH, thus allowing the quaternaryammonium compound to come into contact with biological matter, such aslung tissue, reducing the risks of inhalation, namely risk of toxicity.Under mild acidic conditions, biological matter may be at or near theirrespective isoelectric points. Thus, reducing electrostatic interactionsbetween positively charged cleaning compounds or quaternary ammoniumcompounds with negatively or partially negatively charged biologicalmatter reduces the risk of toxicity and the inhalation risks associatedwith cleaning compounds or quaternary ammonium compounds. Further,inclusion of an acid component within a cleaning compounds or quaternaryammonium compound based cleaning composition is unexpected as cleaningcompounds or quaternary ammonium compounds typically retain theirfunction best neutral or alkaline pH. In an aspect of the invention, theacid component is any compound capable of acting as a proton donor. In afurther aspect of the invention, the acid component is a mineral acid,organic acid, carboxylic acid, amino acid, acidic chelant, and/or acompound capable of acting as a proton donor.

In a further aspect of the invention, at least two acid components areused in compositions according to the invention. Suitable acidcomponents include carboxylic acids, mineral acids, organic acids, aminoacid, acidic chelants, fatty acids, fatty acid surfactants, and/or acompound capable of acting a proton donor, wherein the components may beat least two identical components of any suitable acid componentclassification, at least two components of any suitable acid componentclassification, or at least one component of any suitable acidclassification and at least one component of any different, yet stillsuitable acid classification.

In an aspect, the concentrate compositions include from about 0.1wt.-%-30 wt.-% of an acid component, preferably from about 0.1 wt.-%-25wt.-% of an acid component, and more preferably from about 1.0 wt.-%-20wt.-% of an acid component. In addition, without being limited accordingto the invention, all ranges recited are inclusive of the numbersdefining the range and include each integer within the defined range.

Carboxylic Acid

In an aspect of the invention, the acid component is a carboxylic acid.Generally, carboxylic acids have the formula R-COOH wherein the R mayrepresent any number of different groups including aliphatic groups,alicyclic groups, aromatic groups, heterocyclic groups, all of which maybe saturated or unsaturated as well as substituted or unsubstituted.Carboxylic acids also occur having one, two, three, or more carboxylgroups. Carboxylic acids have a tendency to acidify aqueous compositionsin which they are present as the hydrogen atom of the carboxyl group isactive and may appear as an anion. The carboxylic acid constituentwithin the present composition when combined with aqueous hydrogenperoxide generally functions as an antimicrobial agent as a result ofthe presence of the active hydrogen atom. Moreover, the carboxylic acidconstituent within the invention maintains the composition at an acidicpH. Examples of such carboxylic acids include, but are not limited to,acetic acid, citric acid, succinic acid, adipic acid, hydroxyaceticacid, and lactic acid. One of skill in the art will appreciate thatother carboxylic acids may be used for purposes of the invention.

Mineral Acid

In an aspect of the invention, the acid component is a mineral acid,i.e., an inorganic acid. Examples of such mineral acids include, but arenot limited to, phosphoric acid, sulfamic acid, sulfuric acid, nitricacid, and hydrocholoric acid. Generally, all mineral acids form hydrogenions and the conjugate base ions when dissolved in water. For example,sulfuric acid forms hydrogen sulfate in aqueous solutions via completeionization to form hydronium ions and hydrogen sulfate. Such conjugatebases are also useful acid components for purposes of the invention.

Organic Acid

In an aspect of the invention, the acid component is an organic acid.Suitable organic acids include, but are not limited to, methane sulfonicacid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid,xylene sulfonic acid, cumene sulfonic acid, benzene sulfonic acid,formic acid, acetic acid, mono, di, or tri-halocarboyxlic acids,picolinic acid, dipicolinic acid, and mixtures thereof.

Amino Acid

In an aspect of the invention, the acid component is an amino acidand/or an amino acid derivative. Generally, an amino acid contains anamine functional group and a carboxylic acid functional group, usuallyalong with a side chain group to each amino acid. Suitable amino acidand/or amino acid derivatives include, but are not limited to alanine,arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine,glycine, histidine, isoleucine, leucine, lysine, methionine,phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine,selenocysteine, pyrrolysine, and derivatives thereof.

Acidic Chelant

In an aspect of the invention, the acid component is an acidic chelant.Chelation herein means the binding or complexation of a bi- ormultidentate ligand. These ligands, which are often organic compounds,are called chelants, chelators, chelating agents, and/or sequesteringagent. Chelating agents form multiple bonds with a single metal ion.Chelants, are chemicals that form soluble, complex molecules withcertain metal ions, inactivating the ions so that they cannot normallyreact with other elements or ions to produce precipitates or scale. Theligand forms a chelate complex with the substrate. The term is reservedfor complexes in which the metal ion is bound to two or more atoms ofthe chelant. The chelants for use in the present invention are thosehaving the capability to act a proton donor.

Suitable chelating agents can be selected from the group consisting ofamino carboxylates, amino phosphonates, polyfunctionally-substitutedaromatic chelating agents and mixtures thereof. Preferred chelants foruse herein are chelants such as the amino acids based chelants andpreferably citrate, citrate, tararate, and glutamic-N,N-diacetic acidand derivatives and/or phosphonate based chelants and preferablydiethylenetriamine penta methylphosphonic acid.

Amino carboxylates include ethylenediaminetetra-acetates,N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates,ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates,diethylenetriaminepentaacetates, and ethanoldi-glycines, alkali metal,ammonium, and substituted ammonium salts therein and mixtures therein.As well as MGDA (methyl-glycine-diacetic acid), and salts andderivatives thereof and GLDA (glutamic-N,N-diacetic acid) and salts andderivatives thereof. GLDA (salts and derivatives thereof) is especiallypreferred according to the invention, with the tetrasodium salt thereofbeing especially preferred.

Other suitable chelants include amino acid based compound or a succinatebased compound. The term “succinate based compound” and “succinic acidbased compound” are used interchangeably herein. Other suitable chelantsare described in U.S. Pat. No. 6,426,229. Particular suitable chelantsinclude; for example, aspartic acid-N-monoacetic acid (ASMA), asparticacid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid(ASMP), iminodisuccinic acid (IDS), Imino diacetic acid (IDA),N-(2-sulfomethyl)aspartic acid (SMAS), N-(2-sulfoethyl)aspartic acid(SEAS), N-(2-sulfomethyl)glutamic acid (SMGL), N-(2-sulfoethyl)glutamicacid (SEGL), N-methyliminodiacetic acid (MIDA), alanine-N,N-diaceticacid (ALDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diaceticacid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilicacid-N,N-diacetic acid (ANDA), sulfanilic acid-N,N-diacetic acid (SLDA),taurine-N,N-diacetic acid (TUDA) and sulfomethyl-N,N-diacetic acid(SMDA) and alkali metal salts or ammonium salts thereof. Also suitableis ethylenediamine disuccinate (“EDDS”), especially the [S,S] isomer asdescribed in U.S. Pat. No. 4,704,233. Furthermore,Hydroxyethyleneiminodiacetic acid, Hydroxyiminodisuccinic acid,Hydroxyethylene diaminetriacetic acid is also suitable. Particularlypreferred is alanine. N,N-bis(carboxymethyl)-, trisodium salt.

Other chelants include homopolymers and copolymers of polycarboxylicacids and their partially or completely neutralized salts, monomericpolycarboxylic acids and hydroxycarboxylic acids and their salts.Preferred salts of the abovementioned compounds are the ammonium and/oralkali metal salts, i.e. the lithium, sodium, and potassium salts, andparticularly preferred salts are the sodium salts.

Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic andaromatic carboxylic acids, in which case they contain at least twocarboxyl groups which are in each case separated from one another by,preferably, no more than two carbon atoms. Polycarboxylates whichcomprise two carboxyl groups include, for example, water-soluble saltsof, malonic acid, (ethyl enedioxy) diacetic acid, maleic acid,diglycolic acid, tartaric acid, tartronic acid and fumaric acid.Polycarboxylates which contain three carboxyl groups include, forexample, water-soluble citrate. Correspondingly, a suitablehydroxycarboxylic acid is, for example, citric acid. Another suitablepolycarboxylic acid is the homopolymer of acrylic acid. Preferred arethe polycarboxylates end capped with sulfonates.

Amino phosphonates are also suitable for use as chelating agents andinclude ethylenediaminetetrakis(methylenephosphonates) as DEQUEST.Preferred, these amino phosphonates that do not contain alkyl or alkenylgroups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein such as described in U.S. Pat. No. 3,812,044.Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

Further suitable polycarboxylates chelants for use herein include citricacid, lactic acid, acetic acid, succinic acid, formic acid allpreferably in the form of a water-soluble salt. Other suitablepolycarboxylates are oxodisuccinates, carboxymethyloxysuccinate andmixtures of tartrate monosuccinic and tartrate disuccinic acid such asdescribed in U.S. Pat. No. 4,663,071.

Fatty Acids and Fatty Acid Surfactants

In an aspect of the invention, the acid component is a fatty acid and/orfatty acid surfactant. As used herein, the term “fatty acid” includesany of a group of carboxylic acids that include an alkyl chain. In someembodiments, the alkyl groups can be linear or branched, and saturatedor unsaturated. The chain of alkyl groups contains any length of carbonatoms. In some embodiments, the chain of alkyl groups contains from 4 to12 carbon atoms, 5 to 11 carbon atoms, or 8 to 10 carbon atoms.Exemplary fatty acids can be selected from hexanoic acid, heptanoicacid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, palmiticacid, stearic acid, oleic acid, caproic acid, caprylic acid, capric acidand mixtures thereof. Exemplary longer alkyl chain fatty acids can beselected from for example myristic acid, arachidic acid, behenic acid,lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid,sapienic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidicacid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucicacid, decosahexaenoic acid, gadoleic acid, erucic acid, margaric acid,behenic acid, ricinoleic acid, lignoceric acid, licanic acid,eleostearic acid and mixtures thereof.

In a further aspect, of the invention the acid component is a fatty acidsurfactant. Various exemplary surfactants which are fatty acids aredisclosed in the following section.

Additional Surfactants

In some embodiments, the compositions of the present inventionoptionally include a surfactant. Surfactants suitable for use with thecompositions of the present invention include, but are not limited to,nonionic surfactants, anionic surfactants, and amphoteric surfactants.In some embodiments, the concentrated compositions of the presentinvention include about 0 wt.-% to about 30 wt.-% of a surfactant. Inother embodiments the concentrated compositions of the present inventioninclude about 0.1wt.-% to about 30% of a surfactant. In still yet otherembodiments, the concentrated compositions of the present inventioninclude about 0.5 wt.-% to about 10 wt.-% of a surfactant.

Nonionic Surfactants

Useful additional nonionic surfactants are generally characterized bythe presence of an organic hydrophobic group and an organic hydrophilicgroup and are typically produced by the condensation of an organicaliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with ahydrophilic alkaline oxide moiety which in common practice is ethyleneoxide or a polyhydration product thereof, polyethylene glycol.Practically any hydrophobic compound having a hydroxyl, carboxyl, amino,or amido group with a reactive hydrogen atom can be condensed withethylene oxide, or its polyhydration adducts, or its mixtures withalkoxylenes such as propylene oxide to form a nonionic surface-activeagent. The length of the hydrophilic polyoxyalkylene moiety which iscondensed with any particular hydrophobic compound can be readilyadjusted to yield a water dispersible or water soluble compound havingthe desired degree of balance between hydrophilic and hydrophobicproperties. Useful nonionic surfactants include:

Block polyoxypropylene-polyoxyethylene polymeric compounds based uponpropylene glycol, ethylene glycol, glycerol, trimethylolpropane, andethylenediamine as the initiator reactive hydrogen compound. Examples ofpolymeric compounds made from a sequential propoxylation andethoxylation of initiator are commercially available from BASF Corp. Oneclass of compounds are difunctional (two reactive hydrogens) compoundsformed by condensing ethylene oxide with a hydrophobic base formed bythe addition of propylene oxide to the two hydroxyl groups of propyleneglycol. This hydrophobic portion of the molecule weighs from about 1,000to about 4,000. Ethylene oxide is then added to sandwich this hydrophobebetween hydrophilic groups, controlled by length to constitute fromabout 10% by weight to about 80% by weight of the final molecule.Another class of compounds are tetra-functional block copolymers derivedfrom the sequential addition of propylene oxide and ethylene oxide toethylenediamine. The molecular weight of the propylene oxide hydrotroperanges from about 500 to about 7,000; and, the hydrophile, ethyleneoxide, is added to constitute from about 10% by weight to about 80% byweight of the molecule.

Condensation products of one mole of alkyl phenol wherein the alkylchain, of straight chain or branched chain configuration, or of singleor dual alkyl constituent, contains from about 8 to about 18 carbonatoms with from about 3 to about 50 moles of ethylene oxide. The alkylgroup can, for example, be represented by diisobutylene, di-amyl,polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactantscan be polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols. Examples of commercial compounds of this chemistry areavailable on the market under the trade names Igepal® manufactured byRhone-Poulenc and Triton® manufactured by

Union Carbide.

Condensation products of one mole of a saturated or unsaturated,straight or branched chain alcohol having from about 6 to about 24carbon atoms with from about 3 to about 50 moles of ethylene oxide. Thealcohol moiety can consist of mixtures of alcohols in the abovedelineated carbon range or it can consist of an alcohol having aspecific number of carbon atoms within this range. Examples of likecommercial surfactant are available under the trade names Lutensol™,Dehydol™ manufactured by BASF, Neodol™ manufactured by Shell ChemicalCo. and Alfonic™ manufactured by Vista Chemical Co.

Condensation products of one mole of saturated or unsaturated, straightor branched chain carboxylic acid having from about 8 to about 18 carbonatoms with from about 6 to about 50 moles of ethylene oxide. The acidmoiety can consist of mixtures of acids in the above defined carbonatoms range or it can consist of an acid having a specific number ofcarbon atoms within the range. Examples of commercial compounds of thischemistry are available on the market under the trade names Disponil orAgnique manufactured by BASF and Lipopeg™ manufactured by LipoChemicals, Inc. In addition to ethoxylated carboxylic acids, commonlycalled polyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this invention forspecialized embodiments, particularly indirect food additiveapplications. All of these ester moieties have one or more reactivehydrogen sites on their molecule which can undergo further acylation orethylene oxide (alkoxide) addition to control the hydrophilicity ofthese substances. Care must be exercised when adding these fatty esteror acylated carbohydrates to compositions of the present inventioncontaining amylase and/or lipase enzymes because of potentialincompatibility.

Examples of nonionic low foaming surfactants include:

Compounds from (1) which are modified, essentially reversed, by addingethylene oxide to ethylene glycol to provide a hydrophile of designatedmolecular weight; and, then adding propylene oxide to obtain hydrophobicblocks on the outside (ends) of the molecule. The hydrophobic portion ofthe molecule weighs from about 1,000 to about 3,100 with the centralhydrophile including 10% by weight to about 80% by weight of the finalmolecule. These reverse Pluronics™ are manufactured by BASF Corporationunder the trade name Pluronic™ R surfactants. Likewise, the Tetronic™ Rsurfactants are produced by BASF Corporation by the sequential additionof ethylene oxide and propylene oxide to ethylenediamine. Thehydrophobic portion of the molecule weighs from about 2,100 to about6,700 with the central hydrophile including 10% by weight to 80% byweight of the final molecule.

Compounds from groups (1), (2), (3) and (4) which are modified by“capping” or “end blocking” the terminal hydroxy group or groups (ofmulti-functional moieties) to reduce foaming by reaction with a smallhydrophobic molecule such as propylene oxide, butylene oxide, benzylchloride; and, short chain fatty acids, alcohols or alkyl halidescontaining from 1 to about 5 carbon atoms; and mixtures thereof. Alsoincluded are reactants such as thionyl chloride which convert terminalhydroxy groups to a chloride group. Such modifications to the terminalhydroxy group may lead to all-block, block-heteric, heteric-block orall-heteric nonionics.

Additional examples of effective low foaming nonionics include:

The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issuedSep. 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylenechain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is aninteger of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issuedAug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylenechains and hydrophobic oxypropylene chains where the weight of theterminal hydrophobic chains, the weight of the middle hydrophobic unitand the weight of the linking hydrophilic units each represent aboutone-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178issued May 7, 1968 to Lissant et al. having the general formulaZ[(OR)_(n)OH]_(z) wherein Z is alkoxylatable material, R is a radicalderived from an alkylene oxide which can be ethylene and propylene and nis an integer from, for example, 10 to 2,000 or more and z is an integerdetermined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700, issued May 4, 1954 to Jackson et al. corresponding to theformula Y(C₃H₆O)_(n) (C₂H₄O)_(m)H wherein Y is the residue of organiccompound having from about 1 to 6 carbon atoms and one reactive hydrogenatom, n has an average value of at least about 6.4, as determined byhydroxyl number and m has a value such that the oxyethylene portionconstitutes about 10% to about 90% by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formulaY[(C₃H₆O)_(n) (C₂H₄O)_(m)H]_(x) wherein Y is the residue of an organiccompound having from about 2 to 6 carbon atoms and containing x reactivehydrogen atoms in which x has a value of at least about 2, n has a valuesuch that the molecular weight of the polyoxypropylene hydrophobic baseis at least about 900 and m has value such that the oxyethylene contentof the molecule is from about 10% to about 90% by weight. Compoundsfalling within the scope of the definition for Y include, for example,propylene glycol, glycerine, pentaerythritol, trimethylolpropane,ethylenediamine and the like. The oxypropylene chains optionally, butadvantageously, contain small amounts of ethylene oxide and theoxyethylene chains also optionally, but advantageously, contain smallamounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this invention correspond tothe formula: P[(C₃H₆O)_(n)(C₂H₄O)_(m)H]_(x) wherein P is the residue ofan organic compound having from about 8 to 18 carbon atoms andcontaining x reactive hydrogen atoms in which x has a value of 1 or 2, nhas a value such that the molecular weight of the polyoxyethyleneportion is at least about 44 and m has a value such that theoxypropylene content of the molecule is from about 10% to about 90% byweight. In either case the oxypropylene chains may contain optionally,but advantageously, small amounts of ethylene oxide and the oxyethylenechains may contain also optionally, but advantageously, small amounts ofpropylene oxide.

Polyhydroxy fatty acid amide surfactants suitable for use in the presentcompositions include those having the structural formula R₂CON_(R1)Z inwhich: R1 is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,ethoxy, propoxy group, or a mixture thereof; R₂ is a C₅-C₃₁ hydrocarbyl,which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having alinear hydrocarbyl chain with at least 3 hydroxyls directly connected tothe chain, or an alkoxylated derivative (preferably ethoxylated orpropoxylated) thereof. Z can be derived from a reducing sugar in areductive amination reaction; such as a glycityl moiety.

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 0 to about 25 moles of ethylene oxide are suitable for use inthe present compositions. The alkyl chain of the aliphatic alcohol caneither be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms.

The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylated andpropoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₆-C₁₈ ethoxylated fattyalcohols with a degree of ethoxylation of from 3 to 50.

Suitable nonionic alkylpolysaccharide surfactants, particularly for usein the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from about 6 to about 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside.) The intersaccharide bonds can be, e.g., between the oneposition of the additional saccharide units and the 2-, 3-, 4-, and/or6-positions on the preceding saccharide units.

Fatty acid amide surfactants suitable for use the present compositionsinclude those having the formula: R₆CON(R₇)₂ in which R₆ is an alkylgroup containing from 7 to 21 carbon atoms and each R₇ is independentlyhydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, or —(C₂H₄O)xH, where x is inthe range of from 1 to 3.

A useful class of non-ionic surfactants include the class defined asalkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰— (PO)sN—(EO) _(t)H, R²⁰—(PO)sN—(EO) _(t)H(EO)_(t)H, and R²⁰—N(EO)_(t)H; in which R²⁰ is an alkyl, alkenyl or other aliphatic group, or analkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms, EOis oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2-5, t is1-10, preferably 2-5, and u is 1-10, preferably 2-5. Other variations onthe scope of these compounds may be represented by the alternativeformula: R²⁰—(PO)v-N[(EO) _(w)H][(EO) _(z)H] in which R²⁰ is as definedabove, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and zare independently 1-10, preferably 2-5. These compounds are representedcommercially by a line of products sold by Huntsman Chemicals asnonionic surfactants. A preferred chemical of this class includesSurfonic™ PEA 25 Amine Alkoxylate. Preferred nonionic surfactants forthe compositions of the invention include alcohol alkoxylates, EO/POblock copolymers, alkylphenol alkoxylates, and the like.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed in the practice of the present invention. A typical listing ofnonionic classes, and species of these surfactants, is given in U.S.Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.Further examples are given in “Surface Active Agents and detergents”(Vol. I and II by Schwartz, Perry and Berch).

Semi-Polar Nonionic Surfactants

The semi-polar type of nonionic surface active agents is another classof additional nonionic surfactant useful in compositions of the presentinvention. Generally, semi-polar nonionics are high foamers and foamstabilizers, which can limit their application in CIP systems. However,within compositional embodiments of this invention designed for highfoam cleaning methodology, semi-polar nonionics would have immediateutility. The semi-polar nonionic surfactants include the amine oxides,phosphine oxides, sulfoxides and their alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkalineor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20.

Useful water soluble amine oxide surfactants are selected from thecoconut or tallow alkyl di-(lower alkyl) amine oxides, specific examplesof which are dodecyldimethylamine oxide, tridecyldimethylamine oxide,etradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water solublephosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 toabout 24 carbon atoms in chain length; and, R² and R³ are each alkylmoieties separately selected from alkyl or hydroxyalkyl groupscontaining 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphineoxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphoneoxide, dimethylhexadecylphosphine oxide,diethyl-2-hydroxyoctyldecylphosphine oxide,bis(2-hydroxyethyl)dodecylphosphine oxide, andbis(hydroxymethyl)tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include the watersoluble sulfoxide compounds which have the structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbonatoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxylsubstituents; and R² is an alkyl moiety consisting of alkyl andhydroxyalkyl groups having 1 to 3 carbon atoms.

Useful examples of these sulfoxides include dodecyl methyl sulfoxide;3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methylsulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Semi-polar nonionic surfactants for the compositions of the inventioninclude dimethyl amine oxides, such as lauryl dimethyl amine oxide,myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinationsthereof, and the like. Useful water soluble amine oxide surfactants areselected from the octyl, decyl, dodecyl, isododecyl, coconut, or tallowalkyl di-(lower alkyl) amine oxides, specific examples of which areoctyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamineoxide, undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Suitable nonionic surfactants suitable for use with the compositions ofthe present invention include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, capped EO/POcopolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixturesthereof, or the like. Suitable alkoxylated surfactants for use assolvents include EO/PO block copolymers, such as the Pluronic andreverse Pluronic surfactants; alcohol alkoxylates, such as Dehypon LS-54(R-(EO)₅(PO)₄) and Dehypon LS-36 (R-(EO)₃(PO)₆); and capped alcoholalkoxylates, such as Plurafac LF221 and Tegoten EC11; mixtures thereof,or the like.

Anionic surfactants

Also useful in the present invention are additional surface activesubstances which are categorized as anionics because the charge on thehydrophobe is negative; or surfactants in which the hydrophobic sectionof the molecule carries no charge unless the pH is elevated toneutrality or above (e.g. carboxylic acids). Carboxylate, sulfonate,sulfate and phosphate are the polar (hydrophilic) solubilizing groupsfound in anionic surfactants. Of the cations (counter ions) associatedwith these polar groups, sodium, lithium and potassium impart watersolubility; ammonium and substituted ammonium ions provide both waterand oil solubility; and, calcium, barium, and magnesium promote oilsolubility. As those skilled in the art understand, anionics areexcellent detersive surfactants and are therefore favored additions toheavy duty detergent compositions.

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N-(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxideand nonyl phenol (usually having 1 to 6 oxyethylene groups permolecule).

Anionic sulfonate surfactants suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates),ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleicacid, and the like. Such carboxylates include alkyl ethoxy carboxylates,alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylatesurfactants and soaps (e.g. alkyl carboxyls). Secondary carboxylatesuseful in the present compositions include those which contain acarboxyl unit connected to a secondary carbon. The secondary carbon canbe in a ring structure, e.g. as in p-octyl benzoic acid, or as inalkyl-substituted cyclohexyl carboxylates. The secondary carboxylatesurfactants typically contain no ether linkages, no ester linkages andno hydroxyl groups. Further, they typically lack nitrogen atoms in thehead-group (amphiphilic portion). Suitable secondary soap surfactantstypically contain 11-13 total carbon atoms, although more carbons atoms(e.g., up to 16) can be present. Suitable carboxylates also includeacylamino acids (and salts), such as acylgluamates, acyl peptides,sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyl tauratesand fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula:

R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X   (3)

in which R is a C₈ to C₂₂ alkyl group or

in which R¹ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and Xis a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C₈-C₁₆ alkyl group.In some embodiments, R is a C₁₂-C₁₄ alkyl group, n is 4, and m is 1.

In other embodiments, R is

and R¹ is a C₆-C₁₂ alkyl group. In still yet other embodiments, R¹ is aC₉ alkyl group, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form. Commerciallyavailable carboxylates include, Neodox 23-4, a C₁₂₋₁₃ alkyl polyethoxy(4) carboxylic acid (Shell Chemical), and Emcol CNP-110, a C₉ alkylarylpolyethoxy (10) carboxylic acid (Witco Chemical). Carboxylates are alsoavailable from Clariant, e.g. the product Sandopan® DTC, a C₁₃ alkylpolyethoxy (7) carboxylic acid.

Amphoteric Surfactants

Amphoteric, or ampholytic, surfactants contain both a basic and anacidic hydrophilic group and an organic hydrophobic group. These ionicentities may be any of anionic or cationic groups described herein forother types of surfactants. A basic nitrogen and an acidic carboxylategroup are the typical functional groups employed as the basic and acidichydrophilic groups. In a few surfactants, sulfonate, sulfate,phosphonate or phosphate provide the negative charge.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphato, or phosphono. Amphoteric surfactants are subdivided into twomajor classes known to those of skill in the art and described in“Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71(1989), which is herein incorporated by reference in its entirety. Thefirst class includes acyl/dialkyl ethylenediamine derivatives (e.g.2-alkyl hydroxyethyl imidazoline derivatives) and their salts. Thesecond class includes N-alkylamino acids and their salts. Someamphoteric surfactants can be envisioned as fitting into both classes.

Amphoteric surfactants can be synthesized by methods known to those ofskill in the art. For example, 2-alkyl hydroxyethyl imidazoline issynthesized by condensation and ring closure of a long chain carboxylicacid (or a derivative) with dialkyl ethylenediamine. Commercialamphoteric surfactants are derivatized by subsequent hydrolysis andring-opening of the imidazoline ring by alkylation —for example withchloroacetic acid or ethyl acetate. During alkylation, one or twocarboxy-alkyl groups react to form a tertiary amine and an ether linkagewith differing alkylating agents yielding different tertiary amines.

Long chain imidazole derivatives having application in the presentinvention generally have the general formula:

Neutral pH Zwitterion

wherein R is an acyclic hydrophobic group containing from about 8 to 18carbon atoms and M is a cation to neutralize the charge of the anion,generally sodium. Commercially prominent imidazoline-derived amphotericsthat can be employed in the present compositions include for example:Cocoamphopropionate, Cocoamphocarboxy-propionate, Cocoamphoglycinate,Cocoamphocarboxy-glycinate, Cocoamphopropyl-sulfonate, andCocoamphocarboxy-propionic acid. Amphocarboxylic acids can be producedfrom fatty imidazolines in which the dicarboxylic acid functionality ofthe amphodicarboxylic acid is diacetic acid and/or dipropionic acid.

The carboxymethylated compounds (glycinates) described herein abovefrequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionSurfactants.

Long chain N-alkylamino acids are readily prepared by reaction RNH₂, inwhich R═C₈-C₁₈ straight or branched chain alkyl, fatty amines withhalogenated carboxylic acids.

Alkylation of the primary amino groups of an amino acid leads tosecondary and tertiary amines. Alkyl substituents may have additionalamino groups that provide more than one reactive nitrogen center. Mostcommercial N-alkylamine acids are alkyl derivatives of beta-alanine orbeta-N(2-carboxyethyl) alanine. Examples of commercial N-alkylamino acidampholytes having application in this invention include alkyl beta-aminodipropionates, RN(C₂H₄COOM)₂ and RNHC₂H₄COOM. In an embodiment, R can bean acyclic hydrophobic group containing from about 8 to about 18 carbonatoms, and M is a cation to neutralize the charge of the anion.

Suitable amphoteric surfactants include those derived from coconutproducts such as coconut oil or coconut fatty acid. Additional suitablecoconut derived surfactants include as part of their structure anethylenediamine moiety, an alkanolamide moiety, an amino acid moiety,e.g., glycine, or a combination thereof; and an aliphatic substituent offrom about 8 to 18 (e.g., 12) carbon atoms. Such a surfactant can alsobe considered an alkyl amphodicarboxylic acid. These amphotericsurfactants can include chemical structures represented as:C₁₂-alkyl-C(O)—NH—CH₂—CH₂—N⁺(CH₂—CH₂—CO₂Na)₂—CH₂—CH₂—OH orC₁₂-alkyl-C(O)—N(H)—CH₂—CH₂—N⁺(CH₂—CO₂Na)₂—CH₂—CH₂—OH. Disodiumcocoampho dipropionate is one suitable amphoteric surfactant and iscommercially available under the tradename Miranol™ FBS from RhodiaInc., Cranbury, N.J. Another suitable coconut derived amphotericsurfactant with the chemical name disodium cocoampho diacetate is soldunder the tradename Mirataine™ JCHA, also from Rhodia Inc., Cranbury,N.J.

A typical listing of amphoteric classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated by reference in theirentirety.

Zwitterionic Surfactants

Zwitterionic surfactants can be thought of as a subset of the amphotericsurfactants and can include an anionic charge. Zwitterionic surfactantscan be broadly described as derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Typically, a zwitterionic surfactant includes apositive charged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionics generally contain cationic and anionic groups which ionizeto a nearly equal degree in the isoelectric region of the molecule andwhich can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate.

Betaine and sultaine surfactants are exemplary zwitterionic surfactantsfor use herein. A general formula for these compounds is:

wherein R¹ contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from0 to 1 glyceryl moiety; Y is selected from the group consisting ofnitrogen, phosphorus, and sulfur atoms; R² is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfuratom and 2 when Y is a nitrogen or phosphorus atom, R³ is an alkylene orhydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Zis a radical selected from the group consisting of carboxylate,sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structures listed aboveinclude:4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate;5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate;3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate;3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate;4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate;3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;3-[P,P-dimethyl-P-dodecyl phosphonio]-propane-1-phosphonate; andS[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.The alkyl groups contained in said detergent surfactants can be straightor branched and saturated or unsaturated.

The zwitterionic surfactant suitable for use in the present compositionsincludes a betaine of the general structure:

These surfactant betaines typically do not exhibit strong cationic oranionic characters at pH extremes nor do they show reduced watersolubility in their isoelectric range. Unlike “external” quaternaryammonium salts, betaines are compatible with anionics. Examples ofsuitable betaines include coconut acylamidopropyldimethyl betaine;hexadecyl dimethyl betaine; C₁₂₋₁₄ acylamidopropylbetaine; C₈₋₁₄acylamidohexyldiethyl betaine; 4-C₁₄₋₁₆acylmethylamidodiethylammonio-1-carboxybutane; C₁₆₋₁₈acylamidodimethylbetaine; C₁₂-C₁₆ acylamidopentanediethylbetaine; andC₁₂₋₁₆ acylmethylamidodimethylbetaine.

Sultaines useful in the present invention include those compounds havingthe formula (R(R¹)₂ N⁺ R²SO³⁻, in which R is a C₆-C₁₈ hydrocarbyl group,each R¹ is typically independently C₁-C₃ alkyl, e.g. methyl, and R² is aC₁-C₆ hydrocarbyl group, e.g. a C₁-C₃ alkylene or hydroxyalkylene group.

A typical listing of zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated in their entirety.

Additional Functional Ingredients

The components of the cleaning composition can further be combined withvarious functional components suitable for use in disinfecting andsanitizing applications. For example, in some embodiments few or noadditional functional ingredients are disposed therein.

In other embodiments, additional functional ingredients may be includedin the compositions. The functional ingredients provide desiredproperties and functionalities to the compositions. For the purpose ofthis application, the term “functional ingredient” includes a materialthat when dispersed or dissolved in a use and/or concentrate solution,such as an aqueous solution, provides a beneficial property in aparticular use. Some particular examples of functional materials arediscussed in more detail below, although the particular materialsdiscussed are given by way of example only, and that a broad variety ofother functional ingredients may be used. For example, many of thefunctional materials discussed below relate to materials used incleaning. However, other embodiments may include functional ingredientsfor use in other applications.

In other embodiments, the compositions may include defoaming agents,anti-redeposition agents, bleaching agents, solubility modifiers,dispersants, metal protecting agents, stabilizing agents, corrosioninhibitors, additional sequestrants and/or chelating agents, fragrancesand/or dyes, rheology modifiers or thickeners, hydrotropes or couplers,buffers, solvents and the like.

Exemplary Embodiments

Exemplary ranges of the cleaning compositions according to the inventionin concentrated compositions are shown in Table 3 each in weightpercentage.

TABLE 3 First Exemplary Second Exemplary Third Exemplary Material Rangewt.-% Range wt.-% Range wt.-% Cleaning  1-15 0.1-10  0.001-0.04 Component Polymer 0.0005-0.5   0.001-0.2  0.0001-0.2   Component AcidComponent  0-30 0.1-25   1-20 Surfactant  0-30 0.1-30  0.5-10 Additional Remainder Remainder Remainder Optional Functional Ingredients

According to the invention, the concentrated cleaning compositions setforth in Table 3 have any suitable pH for application of use, includingfrom about 1 to 12.

However, according to aspects of the invention, the concentratedsolution preferably has an acidic to neutral pH depending on aparticular application of use thereof, including from about 0 to 6.Without limiting the scope of invention, the numeric ranges areinclusive of the numbers defining the range and include each integerwithin the defined range.

The cleaning compositions may include concentrate compositions or may bediluted to form use compositions. In general, a concentrate refers to acomposition that is intended to be diluted with water to provide a usesolution that contacts an object to provide the desired cleaning,rinsing, or the like. The cleaning composition that contacts thearticles to be washed or cleaned can be referred to as a concentrate ora use composition (or use solution) dependent upon the formulationemployed in methods according to the invention. It should be understoodthat the concentration of the quaternary ammonium compound, acidcomponent, surfactant, and other optional functional ingredients in thedetergent composition will vary depending on whether the cleaningcomposition is provided as a concentrate or as a use solution.

A use solution may be prepared from the concentrate by diluting theconcentrate with water at a dilution ratio that provides a use solutionhaving desired detersive properties. The water that is used to dilutethe concentrate to form the use composition can be referred to as waterof dilution or a diluent, and can vary from one location to another. Thetypical dilution factor is between approximately 1 and approximately10,000 but will depend on factors including water hardness, the amountof soil to be removed and the like. In an embodiment, the concentrate isdiluted at a ratio of between about 1:10 and about 1:10,000 concentrateto water. Particularly, the concentrate is diluted at a ratio of betweenabout 1:100 and about 1:5,000 concentrate to water. More particularly,the concentrate is diluted at a ratio of between about 1:250 and about1:2,000 concentrate to water.

Manufacturing Methods

Compositions of the invention are prepared by addition of materials. Theanionic surfactant is added to the quaternary ammonium. The quaternaryammonium compound readily couples the more hydrophobic organic acid intosolution with minimal or no agitation.

In some aspects, the compositions according to the invention can be madeby combining the components in an aqueous diluent using commonlyavailable containers and blending apparatus. Beneficially, no specialmanufacturing equipment is required for making the compositionsemploying the quaternary ammonium compounds and the anionic surfactants.A preferred method for manufacturing the cleaning composition of theinvention includes introducing the components into a stirred productionvessel.

The cleaning compositions according to the invention can be provided insingle use or multiple use compositions. In a preferred aspect, thecomposition is a concentrated liquid composition.

Methods Employing Cleaning Compositions of the Invention

The present invention includes methods of using the cleaningcompositions of the present invention for various applications. Theinvention includes a method for reducing a microbial population, amethod for reducing the population of a microorganism on skin and amethod for treating a disease of skin. These methods can operate on anarticle, surface, in a body or stream of water or a gas, or the like, bycontacting the article, surface, body, or stream with a composition ofthe invention. Contacting can include any of numerous methods forapplying a composition of the invention, such as spraying thecompositions, immersing the article in compositions, foam or geltreating the article with the compounds or composition, or a combinationthereof.

In some embodiments, the compositions of the present invention includekilling one or more of the pathogenic bacteria associated with healthcare surfaces and environments including, but not limited to, Salmonellatyphimurium, Staphylococcus aureus, methicillin resistant Staphylococcusaureus, Salmonella choleraesurus, Pseudomonas aeruginosa, Escherichiacoli, mycobacteria, yeast, and mold. The compositions of the inventionhave activity against a wide variety of microorganisms such as Grampositive (for example, Listeria monocytogenes or Staphylococcus aureus)and Gram negative (for example, Escherichia coli or Pseudomonasaeruginosa) bacteria, yeast, molds, bacterial spores, viruses, etc. Thecompounds and compositions of the present invention, as described above,have activity against a wide variety of human pathogens. The presentcompounds and compositions can kill a wide variety of microorganisms ona food processing surface, on the surface of a food product, in waterused for washing or processing of food product, on a health caresurface, or in a health care environment.

The present methods can be used to achieve any suitable reduction of themicrobial population in and/or on the target or the treated targetcomposition. In some embodiments, the present methods can be used toreduce the microbial population in and/or on the target or the treatedtarget composition by at least one log 10. In other embodiments, thepresent methods can be used to reduce the microbial population in and/oron the target or the treated target composition by at least two log 10.In still other embodiments, the present methods can be used to reducethe microbial population in and/or on the target or the treated targetcomposition by at least three log 10. In still other embodiments, thepresent methods can be used to reduce the microbial population in and/oron the target or the treated target composition by at least five log 10.Without limiting the scope of invention, the numeric ranges areinclusive of the numbers defining the range and include each integerwithin the defined range.

The compositions of the invention can be used for a variety of domesticor industrial applications, e.g., to reduce microbial or viralpopulations on a surface or object or in a body or stream of water. Thecompounds can be applied in a variety of areas including kitchens,bathrooms, factories, hospitals, dental offices and food plants, and canbe applied to a variety of hard or soft surfaces having smooth,irregular or porous topography. Suitable hard surfaces include, forexample, architectural surfaces (e.g., floors, walls, windows, sinks,tables, counters and signs); eating utensils; hard-surface medical orsurgical instruments and devices; and hard-surface packaging. Such hardsurfaces can be made from a variety of materials including, for example,ceramic, metal, glass, wood or hard plastic. Suitable soft surfacesinclude, for example paper; filter media; hospital and surgical linensand garments; soft-surface medical or surgical instruments and devices;and soft-surface packaging. Such soft surfaces can be made from avariety of materials including, for example, paper, fiber, woven ornonwoven fabric, soft plastics and elastomers. The compositions of theinvention can also be applied to soft surfaces such as food and skin(e.g., a hand). The present compounds can be employed as a foaming ornon-foaming environmental sanitizer or disinfectant.

The compositions of the invention can be included in products such assterilants, sanitizers, disinfectants, preservatives, deodorizers,antiseptics, fungicides, germicides, sporicides, virucides, detergents,bleaches, hard surface cleaners, hand soaps, waterless hand sanitizers,lubricants, rinse aids, 2-in-1 and/or 3-in-1 products, such asinsecticide/cleaner/sanitizer, 3-sink applications, and pre- orpost-surgical scrubs.

The compositions can also be used in veterinary products such asmammalian skin treatments or in products for sanitizing or disinfectinganimal enclosures, pens, watering stations, and veterinary treatmentareas such as inspection tables and operation rooms. The presentcompositions can be employed in an antimicrobial foot bath for livestockor people.

In some aspects, the compositions of the present invention can beemployed for reducing the population of pathogenic microorganisms, suchas pathogens of humans, animals, and the like. The compounds exhibitactivity against pathogens including fungi, molds, bacteria, spores, andviruses, for example, S. aureus, E. coli, Streptococci, Legionella,Pseudomonas aeruginosa, mycobacteria, tuberculosis, phages, or the like.

Such pathogens can cause a variety of diseases and disorders, includingmastitis or other mammalian milking diseases, tuberculosis, and thelike. Compositions of the present invention can reduce the population ofmicroorganisms on skin or other external or mucosal surfaces of ananimal. In addition, the present compounds can kill pathogenicmicroorganisms that spread through transfer by water, air, or a surfacesubstrate. The compositions need only be applied to the skin, otherexternal or mucosal surfaces of an animal water, air, or surface.

The cleaning compositions can also be used on foods and plant species toreduce surface microbial populations; used at manufacturing orprocessing sites handling such foods and plant species; or used to treatprocess waters around such sites. For example, the compounds can be usedon food transport lines (e.g., as belt sprays); boot and hand-washdip-pans; food storage facilities; anti-spoilage air circulationsystems; refrigeration and cooler equipment; beverage chillers andwarmers, blanchers, cutting boards, third sink areas, and meat chillersor scalding devices. The compositions of the invention can be used totreat produce transport waters such as those found in flumes, pipetransports, cutters, slicers, blanchers, retort systems, washers, andthe like. Particular foodstuffs that can be treated with compounds ofthe invention include eggs, meats, seeds, leaves, fruits and vegetables.Particular plant surfaces include both harvested and growing leaves,roots, seeds, skins or shells, stems, stalks, tubers, corms, fruit, andthe like.

In some aspects, the compositions of the present invention are useful inthe cleaning or sanitizing of containers, processing facilities, orequipment in the food service or food processing industries. Thecompositions have particular value for use on food packaging materialsand equipment, and especially for cold or hot aseptic packaging.Examples of process facilities in which the compound of the inventioncan be employed include a milk line dairy, a continuous brewing system,food processing lines such as pumpable food systems and beverage lines,etc. Food service wares can be disinfected with the compound of theinvention. For example, the compounds can also be used on or in warewash machines, low temperature ware wash machines, dishware, bottlewashers, bottle chillers, warmers, third sink washers, cutting areas(e.g., water knives, slicers, cutters and saws) and egg washers.Particular treatable surfaces include packaging such as cartons,bottles, films and resins; dish ware such as glasses, plates, utensils,pots and pans; ware wash and low temperature ware wash machines; exposedfood preparation area surfaces such as sinks, counters, tables, floorsand walls; processing equipment such as tanks, vats, lines, pumps andhoses (e.g., dairy processing equipment for processing milk, cheese, icecream and other dairy products); and transportation vehicles. Containersinclude glass bottles, PVC or polyolefin film sacks, cans, polyester,PEN or PET bottles of various volumes (100 ml to 2 liter, etc.), onegallon milk containers, paper board juice or milk containers, etc.

Compositions of the present invention can also be employed by dippingfood processing equipment into the use solution, soaking the equipmentfor a time sufficient to sanitize the equipment, and wiping or drainingexcess solution off the equipment, The compound may be further employedby spraying or wiping food processing surfaces with the use solution,keeping the surfaces wet for a time sufficient to sanitize the surfaces,and removing excess solution by wiping, draining vertically, vacuuming,etc.

Compositions of the present invention may also be used in a method ofsanitizing hard surfaces such as institutional type equipment, utensils,dishes, health care equipment or tools, instruments and other hardsurfaces.

The cleaning compositions can be applied to microbes or to soiled orcleaned surfaces using a variety of methods. These methods can operateon an object, surface, in a body or stream of water or a gas, or thelike, by contacting the object, surface, body, or stream with a compoundof the invention. Contacting can include any of numerous methods forapplying a compound, such as spraying the compound, immersing the objectin the compound, foam or gel treating the object with the compound, or acombination thereof.

A concentrate or use concentration of a compound of the presentinvention can be applied to or brought into contact with an object byany conventional method or apparatus for applying an antimicrobial orcleaning compound to an object. For example, the object can be wipedwith, sprayed with, foamed on, and/or immersed in the compound, or a usesolution made from the composition. The composition can be sprayed,foamed, or wiped onto a surface; the composition can be caused to flowover the surface, or the surface can be dipped into the composition.Contacting can be manual or by machine. Food processing surfaces, foodproducts, food processing or transport waters, and the like can betreated with liquid, foam, gel, aerosol, gas, wax, solid, or powderedstabilized compounds according to the invention, or solutions containingthese compounds.

The various methods of treatment according to the invention can includethe use of any suitable level of the cleaning compound. In someembodiments, the treated target composition comprises from about 1 ppmto about 1000 ppm of the cleaning compound when diluted for use. Infurther embodiments, the treated target composition comprises from about1 ppm and about 500 ppm, 5 ppm and about 400 ppm, 10 ppm and about 100ppm, 20 ppm and about 100 ppm, 25 ppm and about 100 ppm, 10 ppm andabout 75 ppm, 20 ppm and about 75 ppm, 25 ppm and about 75 ppm, or about50 ppm of the cleaning compound when diluted for use.

In an aspect, the methods of the invention include generating a usesolution from the concentrated solid or liquid compositions of theinvention. A use solution may be prepared from the concentrate bydiluting the concentrate with water at a dilution ratio that provides ause solution having desired sanitizing and/or other antimicrobialproperties. The water that is used to dilute the concentrate to form theuse composition can be referred to as water of dilution or a diluent,and can vary from one location to another. The typical dilution factoris between approximately 1 and approximately 10,000. In an embodiment,the concentrate is diluted at a ratio of between about 1:10 and about1:10,000 concentrate to water. Particularly, the concentrate is dilutedat a ratio of between about 1:100 and about 1:5,000 concentrate towater. More particularly, the concentrate is diluted at a ratio ofbetween about 1:250 and about 1:2,000 concentrate to water.

In an aspect, a concentrated cleaning composition is diluted to usesolution concentration of about 0.001% (wt/vol.) to about 10% (wt/vol.),or from about 0.001% (wt/vol.) to about 5% (wt/vol.), or from about0.001% (wt/vol.) to about 2% (wt/vol.), or from about 0.01% (wt/vol.) toabout 1% (wt/vol.). Without limiting the scope of invention, the numericranges are inclusive of the numbers defining the range and include eachinteger within the defined range.

Compositions of the invention can be formulated and sold for use as is,or as solvent or solid concentrates. If desired, such concentrates canbe used full-strength as sanitizing rinse compositions. However, theconcentrates typically will be diluted with a fluid (e.g., water) thatsubsequently forms the dilute phase or a use solution. Preferably, theconcentrate forms a single phase before such dilution and remains sowhile stored in the container in which it will be sold. When combinedwith water or other desired diluting fluid at an appropriate dilutionlevel and subjected to mild agitation (e.g., by stirring or pumping thecomposition), some compositions of the invention will form apseudo-stable dispersion, and other compositions of the invention willform a clear or quasi-stable solution or dispersion. If a pseudo-stablecomposition is formed, then the composition preferably remains in thepseudo-stable state for a sufficiently long period so that thecomposition can be applied to a surface before the onset of phaseseparation. The pseudo-stable state need only last for a few secondswhen suitably rapid application techniques such as spraying areemployed, or when agitation during application is employed. Thepseudo-stable state desirably lasts for at least one minute or moreafter mixing and while the composition is stored in a suitable vessel,and preferably lasts for five minutes or more after mixing. Often normalrefilling or replenishment of the applicator (e.g., by dipping theapplicator in the composition) will provide sufficient agitation topreserve the pseudo-stable state of the composition during application.

The various applications of use described herein provide the cleaningcompositions to a surface and/or water source. Beneficially, thecompositions of the invention are fast-acting. However, the presentmethods require a certain minimal contact time of the compositions withthe surface or product in need of treatment for occurrence of sufficientantimicrobial effect. The contact time can vary with concentration ofthe use compositions, method of applying the use compositions,temperature of the use compositions, pH of the use compositions, amountof the surface or product to be treated, amount of soil or substrateson/in the surface or product to be treated, or the like. The contact orexposure time can be about 15 seconds, at least about 15 seconds, about30 seconds or greater than 30 seconds. In some embodiments, the exposuretime is about 1 to 5 minutes. In other embodiments, the exposure time isa few minutes to hours. In other embodiments, the exposure time is a fewhours to days. The contact time will further vary based upon the useconcentration of actives of compositions according to the invention.

Kits for Applications of Use

According to various applications of the compositions according to theinvention a kit may be provided for dosing a composition according tothe invention. In a particular application, the compositions may beprovided by employing a kit according to embodiments of the invention. Akit for dosing and/or providing a cleaning composition according to theinvention may comprise, consist of and/or consist essentially of acleaning component and polymer component (and/or surfactant and/or acidcomponent). Alternatively, the kits may comprise, consist of and/orconsist essentially of a polymer component (and/or surfactant and/oracid component) for dosing with a cleaning component in an applicationof use. The kit may further comprise a measuring means and/or a dosingmeans.

The kit may further comprise additional elements. For example, a kit mayalso include instructions for use of the cleaning compositions.Instructions included in kits can be affixed to packaging material orcan be included as a package insert. While the instructions aretypically written or printed materials they are not limited to such. Anymedium capable of storing such instructions and communicating them to anend user is contemplated by this disclosure. Such media include, but arenot limited to, electronic storage media (e.g., magnetic discs, tapes,cartridges, chips), optical media (e.g., CD, DVD), and the like. As usedherein, the term “instructions” can include the address of an internesite that provides the instructions. The various components of the kitoptionally are provided in suitable containers as necessary, e.g., abottle, jar or vial.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims. Commercial Product A is formulated to include thefollowing raw materials.

The materials used in the following Examples are provided herein:

-   -   Commercial Product A: mixture of alkylbenzyl ammonium chloride        and dialkyl dimethyl ammonium chloride    -   Polymer Component A: cationic flocculant    -   Commercial Product B: mixture of alkylbenzyl ammonium chloride        and dialkyl dimethyl ammonium chloride

Example 1

Comparative studies on the spray pattern of a commercially availablequaternary ammonium chloride with and without the addition of a polymer.Test compositions are shown in Table 4 Composition A is formulatedaccording to the present invention.

TABLE 4 wt % Wt % Polymer Description Active Quat Component A Commercialproduct A 7.5 0.0 Composition A 7.5 0.05

Results from the spray pattern comparison indicated that theformulations according to the present invention provided a stream with awide spray pattern as opposed to a fine mist with a wide spray pattern.The presence of the polymer component therefore reduces the mistingparticles and thereby reduces the inhalation risks.

Example 2

Commercially available quat sanitizers were tested versus a compositionaccording to the claimed invention. Test were performed in water with500 ppm hardness at a temperature of 77° F. Samples contaminated with E.coli and Staph were contacted with each of the compositions for 30seconds. Composition B is formulated according to the present invention.Results are shown in Table 5.

TABLE 5 E. coli E. coli Staph Staph Survivors Survivors SurvivorsSurvivors E. Coli Staph CFU/mL CFU/mL CFU/mL CFU/mL Avg. Log Avg. LogComposition Rep 1 Rep 2 Rep 1 Rep 12 Reduction Reduction Commercial 1e11e1 1e1 1e1 >6.28 >6.38 Product B Composition 1e1 1e1 1e11e1 >6.28 >6.38 B

From the results shown in Table 5, the inclusion of the polymercomponent does not adversely affect micro efficacies. The inclusion ofthe polymer component provides a reduced misting profile which leads tothe quat remaining on the surface to be treated longer. As such, theaddition of the polymer component imparts enhanced residual kill.

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims. The above specification provides a description of themanufacture and use of the disclosed compositions and methods. Sincemany embodiments can be made without departing from the spirit and scopeof the invention, the invention resides in the claims.

What is claimed is:
 1. A cleaning composition, comprising: a quaternaryammonium compound having the formula:

wherein groups R1, R2, R3, and R4 each have a C20 or less chain length,and X- is an anionic counterion; and a polymer component, wherein thepolymer component is a high molecular weight cationic or nonionicpolymer; wherein the composition is either a ready to use solution orwater soluble concentrate and has a pH between about 0 to about
 6. 2.The cleaning composition of claim 1, wherein the quaternary ammoniumcompound is selected from the group consisting of monoalkyltrimethylammonium salts, monoalkyldimethylbenzyl ammonium salts, dialkyldimethylammonium salts, heteroaromatic ammonium salts, polysubstitutedquaternary ammonium salts, bis-quaternary ammonium salts, polymericquaternary ammonium salts, and combinations thereof.
 3. The cleaningcomposition of claim 1, wherein the quaternary ammonium compound ispresent in an amount from about 1 wt.-% to about 50 wt.-%.
 4. Thecleaning composition of claim 1, wherein the polymer component has amolecular weight of 1 million Da to 25 million Da; a particle sizeranging from 0.1 to 10 microns; and a viscosity of 50 to 5000 cPs. 5.The cleaning composition of claim 1, wherein the polymer component is ahigh molecular weight cationic or anionic inversion emulsion polymer. 6.The cleaning composition of claim 1, wherein the polymer component is ahigh molecular weight cationic or anionic dispersion polymer.
 7. Thecleaning composition of claim 1, wherein the polymer component isacrylamide, methacrylamide, acrylic acid or its salts, N-t-butylacrylamide sulfonic acid (ATBS) or its salts, acrylamide tertiary butylsulfonic acid or its salts, 2-(acryloyloxy)-N,N,N-trimethylethananminium(DMAEA.MCQ), diallyldimethylammonium chloride, dimethylaminoethylacrylate methyl chloride quaternary salt,acrylamidopropyltrimethylammonium chloride, dimethylaminoethylmethacrylate methyl chloride quaternary salt,methacrylamidopropyltrimethylammonium chloride, or a combinationthereof.
 8. The cleaning composition of claim 1, further comprising anacid component, wherein the acid component is present in an amount fromabout 0.1 wt.-% to about 30 wt.-%.
 9. The cleaning composition of claim1, wherein the acid component provides the composition with a pH of fromabout 0 to about
 6. 10. The cleaning composition of claim 1, furthercomprising a cleaning component comprising an acid sanitizer.
 11. Thecleaning composition of claim 10, wherein the acid sanitizer comprises acarboxylic acid, peracid, mineral acid, organic acid, amino acid, fatty,acid, linear alkylbenzene, or a combination thereof.
 12. The cleaningcomposition of claim 10, wherein the cleaning component is present in anamount of form about 1 wt.-% to about 15 wt.-%.
 13. The cleaningcomposition of claim 1, further comprising a surfactant comprising ananionic surfactant, nonionic surfactant, amphoteric surfactant or acombination thereof.
 14. The cleaning composition of claim 13, whereinthe surfactant is present in an amount from about 0.1 wt.-% to about 30wt.-%.
 15. The cleaning composition of claim 1, further comprising asolvent.
 16. The cleaning composition of claim 1, wherein the solventcomprises an alcohol alkoxylate, an EO/PO block copolymer, a cappedalcohol alkoxylate, or a combination thereof.
 17. The cleaningcomposition of claim 1, further comprising at least one additionalfunctional ingredient, wherein the additional functional ingredient is athickener, viscosity modifier, solvent, solubility modifier, humectant,metal protecting agent, stabilizing agent, corrosion inhibitor,sequestrant, chelating agent, solidifying agent, sheeting agent, pHmodifying component, fragrance, dye, hydrotrope, coupler, buffer, or acombination thereof.
 18. The cleaning composition of claim 1, whereinthe composition provides an at least 4 log kill on treated surfaceswhile providing reduced inhalation risk.
 19. The cleaning composition ofclaim 1, wherein the composition provides reduced inhalation risk with amedian particle size of the composition is about 11 microns or greater.20. A method of killing microbes comprising: applying to a substrate acleaning composition of claim 1; wherein the composition provides atleast 4 log kill on treated surfaces while providing a reducedinhalation risk.